An organic compound and an organic electroluminescence device including the same

Abstract

This invention relates to a class of organic compounds, and specifically to single-junction and tandem organic light-emitting devices employing these compounds. The compounds of this invention have the structure described below, where Q is selected from substituted or unsubstituted structures shown in formula (Q-1) or (Q-2). When the compounds of this invention are used as electron injection layer materials in single-junction organic light-emitting devices, and as n-type doped layer materials and electron injection layer materials in the connecting layers (n-type doped layer / n-type layer / p-row layer) of stacked organic light-emitting devices, the fabricated devices exhibit excellent stability and high efficiency.

Description

Technical Field

[0001] This invention relates to a class of organic compounds, and also to single-junction and tandem organic electroluminescent devices employing such compounds. Background Technology

[0002] Organic light-emitting diodes (OLEDs) are a type of organic electroluminescent device, mainly consisting of a cathode, an anode, and a light-emitting unit located between the two electrodes. The light-emitting unit is primarily composed of organic semiconductor materials. As an electro-injection type light-emitting device, when a voltage is applied to the electrodes of an OLED device, holes and anodes are injected into the organic functional layer, while electrons are injected from the cathode into the organic functional layer. Electrons and holes recombine in the light-emitting layer to form excitons, ultimately achieving radiative emission. Due to its numerous advantages such as high brightness, fast response, wide viewing angle, low power consumption, and flexibility, OLED devices have received widespread attention in the fields of solid-state display and lighting technology, and are considered one of the most promising display technologies of the 21st century. Currently, this technology has been widely used in display panels for new lighting fixtures, smartphones, and tablets, and will further expand into large-size display products such as televisions. It is a rapidly developing, technologically demanding, and promising new display technology.

[0003] The combination and research of organic functional layers in OLED devices have a crucial impact on device performance. After years of development and research, commonly used functionalized organic materials mainly include: hole injection materials, hole transport materials, hole blocking materials, electron injection materials, electron transport materials, electron blocking materials, as well as luminescent host materials and luminescent guest materials (dyes). Currently, the LUMO energy levels of electron transport materials commonly used in OLEDs are mostly between -2.7 eV and -3.4 eV, while the work functions of metal cathodes such as Al and Ag are greater than 4.0 eV. Therefore, when electrons are injected from the metal cathode to the LUMO energy level of the electron transport layer, a large injection barrier needs to be overcome, resulting in a high driving voltage and a situation where electrons are minority carriers and holes are majority carriers. This carrier imbalance significantly reduces device efficiency and lifetime. To reduce the electron injection barrier and improve the efficiency and lifetime of OLED devices, alkali metal compounds such as Liq are widely used as n-type dopants, combined with nitrogen-containing aromatic ring electron transport materials and Al electrodes to improve device efficiency and operating lifetime. According to currently available literature, the mechanism by which alkali metal compound n-type dopants such as LiF and Liq lower the electron injection barrier mainly lies in the fact that during the deposition of Al electrodes, due to the presence of Al and nitrogen-containing aromatic ring electron transport materials (ETM), Liq reacts with Al and ETM to produce Li. + ETM - Because of Li+ ETM - The presence of alkali metal compounds significantly reduces the work function on the cathode side, improving the electron injection performance of OLED devices. Therefore, OLED devices using alkali metal compounds such as LiF and Liq as n-type dopants exhibit low operating voltage and high luminous efficiency. However, alkali metal compound electron injection materials like LiF and Liq often require Al electrodes and nitrogen-containing aromatic ring electron transport materials to achieve good electron injection performance, greatly limiting their application in top-emitting and inverted devices. Furthermore, device lifetime still needs improvement, thus limiting their application in industrial production. Developing new high-performance electron injection materials is of great significance for further improving and expanding the applications of OLED devices.

[0004] In recent years, OLED devices with a tandem structure have attracted widespread attention. The light-emitting principle of tandem OLED devices is similar to that of traditional single-layer OLED devices. The difference lies in that tandem OLED devices consist of multiple light-emitting units connected in series by a connecting layer. This connecting layer acts like an electrode, generating charge carriers in pairs under the drive of an external electric field. These generated charge carriers can be further separated and injected into adjacent light-emitting units. Due to this tandem device structure, each injected electron or hole can generate a photon and achieve radiative emission in each light-emitting unit. Therefore, for a tandem OLED device containing N light-emitting units, its current efficiency is approximately N times that of a single-layer OLED device. To achieve the same brightness, the current density required for tandem OLED devices is significantly reduced, thus helping to improve the efficiency roll-off and lifetime issues of OLED devices.

[0005] Currently, a commonly used interconnect layer structure in tandem OLED devices is an n-type doped layer / n-type layer / p-type layer. The energy level difference between the LUMO level of the n-type layer and the HOMO level of the p-type layer is small, allowing for efficient carrier generation at relatively low driving voltages. The dopant in the n-type doped layer is primarily composed of alkali or alkaline earth metals with low work function (WF < 3.0 eV), including lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), magnesium (Mg), and calcium (Ca). However, these alkali or alkaline earth metal n-type dopants tend to diffuse towards the p-type doped layer under an external electric field, leading to an increase in driving voltage during operation, a significant decrease in device lifetime, and severely impacting device efficiency and stability.

[0006] In recent years, an n-type doping strategy based on transition metal coordination has provided a new solution for developing efficient and stable electron injection materials and tandem device interconnect layers. This strategy can be used to construct electron injection layers and interconnect layers for OLED devices, enabling the fabrication of high-efficiency, long-lifetime OLED devices with broad development prospects. By doping transition metals (Ag, Cu, etc.) into coordination-capable o-phenanthroline-based organic materials (represented by B-Phen), the coordination reaction between the o-phenanthroline-based materials and the transition metal promotes the loss of electrons by the metal. Therefore, o-phenanthroline-based organic materials can be combined with transition metals (Ag, Cu, etc.) as electron injection layers for OLED devices, significantly reducing the work function of the cathode and the electron injection barrier, thereby significantly improving device efficiency and lifetime while reducing the device's driving voltage. Summary of the Invention

[0007] Studies have found that the structure, coordination, and transport properties of o-phenanthroline-based electron injection materials have a significant impact on the performance and applications of OLED devices. The purpose of this invention is to provide an organic compound and apply this compound as an organic functional material in single-junction and tandem organic electroluminescent devices, thereby effectively reducing the driving voltage, improving device luminous efficiency and lifetime, and solving the problems existing in the prior art.

[0008] Specifically, the present invention provides an organic compound having the structure shown in formula (1);

[0009]

[0010] In equation (1), ring C represents a benzene ring that is absent or fused with rings A and B. When ring C is absent, rings A and B are connected by a single bond.

[0011] R1, R2, R3, R4, and R5 are independently selected from hydrogen, deuterium, halogen, cyano, unsubstituted or R'-substituted C1-C30 chain alkyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C1-C30 alkoxy, unsubstituted or R'-substituted C4-C30 alkylsilyl, and unsubstituted or R'-substituted C2-C30... One of the following: alkylamino, unsubstituted or R'-substituted C4-C30 cycloalkylamino, unsubstituted or R'-substituted C6-C30 arylamino, unsubstituted or R'-substituted C3-C30 heteroarylamino, unsubstituted or R'-substituted C6-C30 aryloxy, unsubstituted or R'-substituted C6-C60 arylboryl, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl;

[0012] R' is selected from one of the following: deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy, C4-C10 alkylsilyl, C2-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C6-C60 arylboryl, C6-C60 aryl, and C3-C60 heteroaryl.

[0013] Q represents a bridging group, and n is an integer from 2 to 8;

[0014] Q is selected from the structure shown in formula (Q-1) or (Q-2) below, with or without substitution:

[0015]

[0016] In equations (Q-1) and (Q-2), X is selected from C, Si, or B, and Y is selected from C or N;

[0017] "—*" represents the connection site of Q in equation (1), and the number of "—*" is consistent with the selected value of n;

[0018] The “—” symbol is used to represent the loop structure, indicating that the connection point is located at any position on the loop structure where bonding can occur.

[0019] When Q has a substituent, the substituent is selected from one of the following: deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy, C4-C10 alkylsilyl, C2-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C6-C60 arylboryl, C6-C60 aryl, and C3-C60 heteroaryl.

[0020] More preferably, Q is selected from one of the following groups, substituted or unsubstituted:

[0021]

[0022] More preferably, Q is selected from substituted or unsubstituted structures as shown below:

[0023]

[0024] When Q has a substituent, the substituent is selected from one of deuterium, halogen, cyano, C1-C5 chain alkyl, C3-C5 cycloalkyl, C1-C5 alkoxy, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C60 aryl, and C3-C60 heteroaryl.

[0025] Further preferably, n is 2, 3 or 4; most preferably, n is 2.

[0026] In the general formula compound of the present invention, preferably R1, R2, R3, R4, and R5 are each independently selected from one or a combination of two of the following: hydrogen, deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C1-C10 alkoxy, C4-C10 alkylsilyl, C2-C10 alkylamino, C4-C10 cycloalkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C6-C60 arylboryl, C6-C60 aryl, and C3-C60 heteroaryl.

[0027] More preferably, R1, R2, R3, R4, and R5 are each independently selected from hydrogen, deuterium, methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, 2-ethylhexyl, dimethylamino, tetrahydropyrrolyl, piperidinyl, cyclohexylimino, cycloheptylimino, cyclooctylimino, methoxy, ethoxy, propoxy Butoxy, phenoxy, phenyl, naphthyl, anthracene, benzo[a]anthracene, phenanthrene, benzo[a]phenanthrene, pyrene, fenyl, peryl, fluoranthyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, amphylphenyl, terphenyl, triphenyl, trimeric phenyl, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorenyl, trimerinyl, isotrimericininyl, spirotrimericininyl, spiroisotrimericininyl, furanyl, benzo[a]furanyl, isobenzo[a]furanyl, dibenzo[a]furanyl Thiophene, benzothiophene, isobenzothiophene, dibenzothiophene, pyrrole, isoindolyl, carbazole, tert-butylcarbazole, indocarbazole, tetrahydroacridyl, phenylmercapto, phenol, naphthiomercapto, naphthol, anthrathiomercapto, anthrathol, indazole, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrathoxazolyl, benzoxazolyl, anthrathoxazolyl, phenanthoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, 1,5-diazolyl One or a combination of two of the following: xanthyl, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrene, pyrazinyl, phenazinyl, phenoxazinyl, phenthiazinyl, naphridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinel, purinel, pteridinyl, inazinyl, 1,5,7-triazabicyclo[4.4.0]dec-5-enyl, and 4-methoxyphenyl.

[0028] It should be noted that, unless otherwise defined below, all technical and scientific terms used herein are intended to have the same meaning as commonly understood by one of those skilled in the art. References to technical intent herein refer to technology as commonly understood in the art, including variations or equivalent substitutions of technology that are obvious to one of those skilled in the art.

[0029] In this specification, the expression Ca to Cb represents the number of carbon atoms in the group as a to b. Unless otherwise specified, this number of carbon atoms generally does not include the number of carbon atoms in the substituents. When describing C1 to C30, it includes, but is not limited to, C1, C2, C3, C4, C3, C6, C7, C8, C9, C10, C11, C12, C13, C14, C15, C16, C17, C18, C19, C20, C22, C24, C26, C28, etc. Other numerical ranges are not elaborated.

[0030] The terms “including,” “comprising,” “having,” “containing,” or “involving,” and their other variations herein, are inclusive or open-ended and do not exclude other unlisted elements or method steps.

[0031] In this specification, "each independently" means that when there are multiple subjects, they may be the same or different from each other.

[0032] In this invention, heteroatoms generally refer to atoms or groups of atoms selected from B, N, O, S, P, Si and Se, and are preferably selected from B, N, O and Si.

[0033] As used herein, the terms “heterocyclic group” and “heterocycle” refer to a saturated (i.e., heterocyclic alkyl) or partially unsaturated (i.e., having one or more double and / or triple bonds within the ring) cyclic group having at least one ring atom selected from N, O and S and the remaining ring atoms being C.

[0034] As used herein, the terms “(aryl)aryl” and “aromatic ring” refer to an all-carbon monocyclic or fused-ring polycyclic aromatic group having a conjugated π-electron system. As used herein, the terms “(heteroaryl)aryl” and “heteroaromatic ring” refer to monocyclic, bicyclic, or tricyclic aromatic ring systems. As used herein, the term “aralkyl” preferably means an aryl or heteroaryl-substituted alkyl group, wherein the aryl, heteroaryl, and alkyl groups are as defined herein.

[0035] In this specification, unless otherwise specified, the description of chemical elements usually includes the concept of isotopes with the same chemical properties. For example, carbon (C) includes 12C, 13C, etc., which will not be elaborated further.

[0036] The term "substitution" refers to the selective replacement of one or more (e.g., one, two, three, or four) hydrogen atoms on a specified atom by a designated group, provided that the substitution does not exceed the normal valence of the specified atom in the present case and that the substitution forms a stable compound. Combinations of substituents and / or variables are permitted only if such combinations form a stable compound.

[0037] If a substituent is described as being “independently selected” from a group, then each substituent is selected independently of the others. Therefore, each substituent may be the same as or different from another (other) substituent.

[0038] As used herein, the term "one or more" means one or more under reasonable conditions, such as two, three, four, five, or ten.

[0039] Unless otherwise specified, as used herein, the connection point of a substituent may be derived from any suitable location of the substituent.

[0040] When the bond of a substituent is such that it passes through the ring and connects two atoms, then such a substituent can be bonded to any cyclic atom in the substituted ring.

[0041] The term “about” means within ±10% of the stated value, preferably within ±5%, and more preferably within ±2%.

[0042] In the structural formulas disclosed in this specification, the way the ring structure is represented by "—" indicates that the connection point is located at any position on the ring structure where bonding can occur.

[0043] The aforementioned monocyclic aryl groups refer to molecules containing one or at least two phenyl groups. When a molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by single bonds, such as phenyl, diphenyl, and terphenyl. Fused-ring aryl groups refer to molecules containing at least two benzene rings, but the benzene rings are not independent of each other, but are fused together by sharing ring edges, such as naphthyl and anthracene. Monocyclic heteroaryl groups refer to molecules containing at least one heteroaryl group. When a molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are independent of each other and connected by single bonds, such as pyridine, furan, and thiophene. Fused-ring heteroaryl groups refer to molecules formed by the fusion of at least one phenyl group and at least one heteroaryl group, or by the fusion of at least two heteroaryl rings, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, and dibenzothiophene.

[0044] Unless otherwise specified, the C6-C60 aromatic rings (or C6-C50 aromatic rings) and C3-C60 heteroaromatic rings (or C3-C50 heteroaromatic rings) mentioned above in this invention refer to aromatic groups that satisfy the π-conjugated system, including both monocyclic residues and fused ring residues. A monocyclic residue refers to a molecule containing at least one phenyl group. When a molecule contains at least two phenyl groups, the phenyl groups are independent of each other and connected by a single bond, such as phenyl, diphenyl, and terphenyl. A fused-ring residue refers to a molecule containing at least two benzene rings, but the benzene rings are not independent of each other, but are fused together by sharing a ring edge, such as naphthyl, anthracene, and phenanthrene. A monocyclic heteroaryl group refers to a molecule containing at least one heteroaryl group. When a molecule contains one heteroaryl group and other groups (such as aryl, heteroaryl, alkyl, etc.), the heteroaryl group and other groups are independent of each other and connected by a single bond, such as pyridine, furan, and thiophene. A fused-ring heteroaryl group refers to a molecule formed by the fusion of at least one phenyl group and at least one heteroaryl group, or by the fusion of at least two heteroaryl rings, such as quinoline, isoquinoline, benzofuran, dibenzofuran, benzothiophene, and dibenzothiophene.

[0045] In this specification, the substituted or unsubstituted C6-C60 aromatic ring (or C6-C50 aromatic ring) is preferably a C6-C30 aromatic ring, more preferably an aromatic ring from the group consisting of phenyl, naphthyl, anthracene, benzo[a]anthrayl, phenanthryl, benzo[a]phenanthryl, pyrene, pyrene, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, azophenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthryl, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorenyl, trimenyl, isotriinyl, spirotriinyl, and spiroisotriinyl. Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, meta-terphenyl-4-yl, meta-terphenyl-3-yl, and meta-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracene group is selected from 1-anthrayl, 2-anthrayl, and 9-anthrayl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrene group is selected from 1-pyrene, 2-pyrene, and 4-pyrene; and the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl. Preferred examples of aromatic rings in this invention include those composed of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, indene, fluorenyl and their derivatives, fluoranyl, triphenylene, pyrene, perylene, etc. The group is selected from the group consisting of 1-triphenyl-4-yl, 3-triphenyl-3-yl, 2-triphenyl-2-yl, 4-triphenyl-3-yl, 3-triphenyl-4-yl, 3-triphenyl-3-yl, and 3-triphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracene group is selected from the group consisting of 1-anthrayl, 2-anthrayl, and 9-anthrayl. The fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorenyl, 9,9-spirodifluorenyl, and benzo[a]fluorenyl; the pyrene group is selected from the group consisting of 1-pyrene, 2-pyrene, and 4-pyrene; and the tetraphenyl group is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl.

[0046] In this specification, the substituted or unsubstituted C6-C60 aryl (or C6-C50 aryl) is preferably C6-C30 aryl, more preferably a group from the group consisting of phenyl, naphthyl, anthracene, benzo[a]anthrayl, phenanthryl, benzo[a]phenanthryl, pyrene, pyrene, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, azophenyl, terphenyl, triphenyl, tetraphenyl, fluorenyl, spirodifluorenyl, dihydrophenanthryl, dihydropyrene, tetrahydropyrene, cis or trans indo[a]fluorenyl, trimenyl, isotrimeric indo[a], spirotrimeric indo[a], and spiroisotrimeric indo[a] Specifically, the biphenyl group is selected from 2-biphenyl, 3-biphenyl, and 4-biphenyl; the terphenyl group includes p-terphenyl-4-yl, p-terphenyl-3-yl, p-terphenyl-2-yl, meta-terphenyl-4-yl, meta-terphenyl-3-yl, and meta-terphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracene group is selected from 1-anthrayl, 2-anthrayl, and 9-anthrayl; the fluorenyl group is selected from 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the pyrene group is selected from 1-pyrene, 2-pyrene, and 4-pyrene; and the tetraphenyl group is selected from 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl. Preferred examples of aryl groups in this invention include those composed of phenyl, biphenyl, terphenyl, naphthyl, anthracene, phenanthryl, indene, fluorenyl and their derivatives, fluoranyl, triphenylene, pyrene, perylene, etc. The group is selected from the group consisting of 1-triphenyl-4-yl, 3-triphenyl-3-yl, 2-triphenyl-2-yl, 4-triphenyl-3-yl, 3-triphenyl-4-yl, 3-triphenyl-3-yl, and 3-triphenyl-2-yl; the naphthyl group includes 1-naphthyl or 2-naphthyl; the anthracene group is selected from the group consisting of 1-anthrayl, 2-anthrayl, and 9-anthrayl. The fluorenyl group is selected from the group consisting of 1-fluorenyl, 2-fluorenyl, 3-fluorenyl, 4-fluorenyl, and 9-fluorenyl; the fluorenyl derivative is selected from the group consisting of 9,9-dimethylfluorenyl, 9,9-spirodifluorenyl, and benzo[a]fluorenyl; the pyrene group is selected from the group consisting of 1-pyrene, 2-pyrene, and 4-pyrene; the tetraphenyl group is selected from the group consisting of 1-tetraphenyl, 2-tetraphenyl, and 9-tetraphenyl. The C6-C60 aryl (or C6-C50 aryl) groups of the present invention can also be groups formed by single bond linkage and / or fusion of the above groups.

[0047] In this specification, the substituted or unsubstituted C3-C60 heteroaryl ring (or C3-C50 heteroaryl ring) is preferably a C3-C30 heteroaryl ring, which can be a nitrogen-containing heteroaryl, an oxygen-containing heteroaryl, a sulfur-containing heteroaryl, etc. Specific examples include: furanyl, thiophene, pyrrole, pyridyl, benzofuranyl, benzothiophene, isobenzofuranyl, isobenzothiophene, indolyl, isoindolyl, dibenzofuranyl, dibenzothiophene, carbazole and its derivatives, quinolinyl, isoquinoline. acridine, phenanthridine, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, phenthiazinyl, phenazinyl, pyrazolyl, indazole, imidazole, benzimidazole, naphthiazinyl, phenanthiazinyl, pyridinium-imidazolyl, pyrazinium-imidazolyl, quinoxalinium-imidazolyl, oxazolyl, benzoxoxazolyl, naphthoxoxazolyl, anthraquinoneium-oxazolyl, phenanthoxoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzopyridazine 1,5-diazaphenanthyl, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetrazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinel, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3-oxadiazolyl Heteroaromatic rings formed by 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purine, pteridine, indazinyl, benzothiadiazole, etc. As a preferred example of the heteroaromatic ring in this invention, it is a heteroaromatic ring of furanyl, thiopheneyl, pyrroleyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl and its derivatives, wherein the carbazoleyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole or indolocarbazole.

[0048] In this specification, the substituted or unsubstituted C3-C60 heteroaryl (or C3-C50 heteroaryl) is preferably a C3-C30 heteroaryl, more preferably a nitrogen-containing heteroaryl, an oxygen-containing heteroaryl, a sulfur-containing heteroaryl, etc. Specific examples include: furanyl, thiophene, pyrrole, pyridyl, benzofuranyl, benzothiophene, isobenzofuranyl, isobenzothiophene, indolyl, isoindolyl, dibenzofuranyl, dibenzothiophene, carbazole and its derivatives, quinolinyl, isoquinoline, etc. Linolyl, acridineyl, phenanthridineyl, benzo-5,6-quinolinyl, benzo-6,7-quinolinyl, benzo-7,8-quinolinyl, phenthiazinyl, phenazinyl, pyrazolyl, indazoleyl, imidazolyl, benzimidazoleyl, naphthiazinyl, phenanthiazinyl, pyridinium-imidazolyl, pyrazinium-imidazolyl, quinoxalinium-imidazolyl, oxazolyl, benzoxoxazolyl, naphthoxoxazolyl, anthraquinoneium-oxazolyl, phenanthoxoxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, pyridazinyl, benzyl pyridazinyl, pyrimidinyl, benzopyrimidinyl, quinoxalinyl, 1,5-diazathanel, 2,7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetrazaperyl, pyrazinyl, phenazinyl, phenothiazinyl, naphridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinel, 1,2,3-triazolyl, 1,2,4-triazolyl, benzotriazolyl, 1,2,3 -Oxadiazolyl, 1,2,4-oxadiazolyl, 1,2,5-oxadiazolyl, 1,2,3-thiadiazolyl, 1,2,4-thiadiazolyl, 1,2,5-thiadiazolyl, 1,3,4-thiadiazolyl, 1,3,5-triazinyl, 1,2,4-triazinyl, 1,2,3-triazinyl, tetrazolyl, 1,2,4,5-tetrazinyl, 1,2,3,4-tetrazinyl, 1,2,3,5-tetrazinyl, purine, pteridine, indazinyl, benzothiadiazole, etc. Preferred examples of heteroaryl groups in this invention include furanyl, thiopheneyl, pyrroleyl, benzofuranyl, benzothiopheneyl, isobenzofuranyl, indolyl, dibenzofuranyl, dibenzothiopheneyl, carbazoleyl, and their derivatives. The carbazoleyl derivative is preferably 9-phenylcarbazole, 9-naphthylcarbazole, benzocarbazole, dibenzocarbazole, or indolocarbazole. The C3-C60 heteroaryl groups (or C3-C50 heteroaryl groups) of this invention can also be groups formed by single-bonded or / and fused combinations of the above groups.

[0049] In this invention, aryloxy and heteroaryloxy groups can be exemplified by the groups formed by the above-mentioned aryl and heteroaryl groups with oxygen. In this invention, arylamino and heteroarylamino groups can be exemplified by the groups formed by the substitution of one or both H atoms in the above-mentioned aryl and heteroaryl groups for the -NH2 group.

[0050] In this specification, examples of C1-C20 straight-chain or branched alkyl groups include: methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, neopentyl, n-hexyl-neohexyl, n-heptyl, n-octyl, 2-ethylhexyl, etc. Examples of C1-C20 chain haloalkyl groups include: trifluoromethyl, pentafluoroethyl, 2,2,2-trifluoroethyl, etc.

[0051] In this specification, C3 to C20 cycloalkyl groups include monocycloalkyl and polycycloalkyl groups, and specific examples include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclohexyl, cycloheptyl, cyclooctyl, adamantyl, etc.

[0052] In this specification, alkoxy refers to a group composed of straight-chain or branched alkyl groups and oxygen, or a group composed of cycloalkyl groups and oxygen.

[0053] Examples of C1 to C20 alkoxy groups include: methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, pentooxy, isopentoxy, hexoxy, heptoxy, octoxy, nonoxy, decoxy, undecoxy, dodecoxy, etc., among which methoxy, ethoxy, n-propoxy, isopropoxy, tert-butoxy, sec-butoxy, isobutoxy, isopentoxy, and isopentoxy are preferred, and methoxy is more preferred.

[0054] In this specification, examples of C1-C20 alkylsilyl groups can be silyl groups substituted with groups listed in the C1-C20 alkyl groups, that is, groups formed by substituting one, two, or three hydrogens on a silyl group with a straight-chain or branched alkyl or cycloalkyl group. Specific examples include: methylsilyl, dimethylsilyl, trimethylsilyl, ethylsilyl, diethylsilyl, triethylsilyl, tert-butyldimethylsilyl, tert-butyldiphenylsilyl, and other groups.

[0055] Furthermore, among the general formula compounds of the present invention, the following specific structural compounds E-1 to E-765 are preferred, and these compounds are merely representative:

[0056]

[0057]

[0058]

[0059]

[0060]

[0061]

[0062]

[0063]

[0064]

[0065]

[0066]

[0067]

[0068]

[0069]

[0070]

[0071]

[0072]

[0073]

[0074]

[0075]

[0076]

[0077]

[0078]

[0079]

[0080]

[0081]

[0082]

[0083]

[0084]

[0085]

[0086]

[0087]

[0088]

[0089]

[0090]

[0091]

[0092]

[0093]

[0094]

[0095]

[0096]

[0097]

[0098]

[0099]

[0100]

[0101]

[0102]

[0103]

[0104] Another object of the present invention is to protect the application of the compounds of the above general formula (1), which is as an electron injection material in single-junction organic light-emitting devices, and as an n-type doped layer material and electron injection material in the connecting layer (n-type doped layer / n-type layer / p-type layer) in tandem organic light-emitting devices. Furthermore, the application field of the compounds of the present invention is not limited to organic light-emitting materials, but can be further extended to the technical fields of perovskite and quantum dot light-emitting diodes, optical sensors, solar cells, organic thin-film transistors, etc.

[0105] This invention provides a single-junction organic electroluminescent device, comprising a substrate and an anode layer, a plurality of light-emitting functional layers, and a cathode layer sequentially formed on the substrate, characterized in that the light-emitting functional layers comprise a compound shown in the above general formula (1):

[0106]

[0107] In equation (1), ring C represents a benzene ring that is absent or fused with rings A and B. When ring C is absent, rings A and B are connected by a single bond.

[0108] R1, R2, R3, R4, and R5 are independently selected from hydrogen, deuterium, halogen, cyano, unsubstituted or R'-substituted C1-C30 chain alkyl, unsubstituted or R'-substituted C3-C20 cycloalkyl, unsubstituted or R'-substituted C2-C20 alkenyl, unsubstituted or R'-substituted C1-C30 alkoxy, unsubstituted or R'-substituted C4-C30 alkylsilyl, and unsubstituted or R'-substituted C2-C30... One of the following: alkylamino, unsubstituted or R'-substituted C4-C30 cycloalkylamino, unsubstituted or R'-substituted C6-C30 arylamino, unsubstituted or R'-substituted C3-C30 heteroarylamino, unsubstituted or R'-substituted C6-C30 aryloxy, unsubstituted or R'-substituted C6-C60 arylboryl, unsubstituted or R'-substituted C6-C60 aryl, and unsubstituted or R'-substituted C3-C60 heteroaryl;

[0109] R' is selected from one of the following: deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy, C4-C10 alkylsilyl, C2-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C6-C60 arylboryl, C6-C60 aryl, and C3-C60 heteroaryl.

[0110] n is an integer between 2 and 8; Q is selected from the substituted or unsubstituted structures shown in equation (Q-1) or (Q-2) below:

[0111]

[0112] In equations (Q-1) and (Q-2), X is selected from C, Si, or B, and Y is selected from C or N;

[0113] "—*" represents the connection site of Q in equation (1), and the number of "—*" is consistent with the selected value of n;

[0114] The “—” symbol is used to represent the loop structure, indicating that the connection point is located at any position on the loop structure where bonding can occur.

[0115] When Q has a substituent, the substituent is selected from one of the following: deuterium, halogen, cyano, C1-C10 chain alkyl, C3-C10 cycloalkyl, C2-C10 alkenyl, C1-C10 alkoxy, C4-C10 alkylsilyl, C2-C10 alkylamino, C6-C30 arylamino, C3-C30 heteroarylamino, C6-C30 aryloxy, C6-C60 arylboryl, C6-C60 aryl, and C3-C60 heteroaryl.

[0116] Specifically, the light-emitting functional layer includes a light-emitting layer and an electron injection layer, and further includes one or more of a hole injection layer, a hole transport layer, and an electron transport layer. The hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the light-emitting layer is formed on the hole transport layer, the electron transport layer is formed on the light-emitting layer, the electron injection layer is formed on the electron transport layer, and the cathode layer is formed on the electron injection layer. The electron injection layer includes at least one of the general formula compounds and preferred specific compounds of the present invention shown above.

[0117] This invention provides a tandem organic electroluminescent device, comprising the following structure: an anode, a cathode, at least two electroluminescent units disposed between the anode and the cathode, and a connecting layer disposed between adjacent electroluminescent units. Each electroluminescent unit includes at least one electron transport layer and one organic light-emitting layer. The connecting layer is characterized by being a multi-layered structure, including an n-type doped layer, an n-type layer, and a p-type layer; the n-type doped layer includes at least one compound of the general formula of this invention shown above and a preferred specific compound. The electron injection layer is formed on the last light-emitting unit, i.e., below the cathode.

[0118] Further preferably, in the single-junction and tandem organic electroluminescent devices of the present invention, both the n-type doped layer and the electron injection layer contain the compound of the present invention and the n-type dopant. The n-type dopant is mainly composed of alkali metals, alkaline earth metals, and some transition metals and their salts, including but not limited to one or a mixture of several of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), magnesium (Mg), calcium (Ca), iron (Fe), chromium (Cr), niobium (Nb), cobalt (Co), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), tungsten (W), rhenium (Re), platinum (Pt), gold (Au), and ytterbium (Yb). Further preferably, the n-type dopant is Zn, Ag, Cu, Au, or Yb.

[0119] In the organic electroluminescent device of the present invention, the n-type doped layer in the electron injection layer and the connecting layer includes an n-doperant and the compound of the present invention with a doping ratio of 0.1 wt% to 50 wt%, and the corresponding doping ratio (volume fraction) is 0.01 vol% to 5 vol%.

[0120] Preferably, the doping ratio of the n-doper to the compound of the present invention is from 0.05 wt% to 20 wt%.

[0121] In the single-junction and series organic electroluminescent devices of the present invention, the thickness of the n-type doped layer in the electron injection layer and the connecting layer is 0.1 nm-20 nm; preferably, the thickness of the electron injection layer is 3-5 nm, and the thickness of the n-type doped layer in the connecting layer is 1-10 nm.

[0122] When the compounds of the present invention are applied to the electron injection layer of organic electroluminescent devices and the interconnecting layer of multilayer devices, the devices can achieve higher luminous efficiency and longer lifetime. The following are the inventors' speculations, but these speculations do not limit the scope of protection of the present invention.

[0123] First, the bridging group Q in the specific compounds of this invention has a relatively large molecular weight, which helps to increase the glass transition temperature of the organic ligands. Furthermore, by incorporating metals such as Ag and Yb, the morphological stability during long-term device operation can be effectively enhanced, thus improving device lifetime. Second, when the bridging group in this invention uses groups with good electron transport properties, such as spirofluorene, the transport properties of the organic ligands can be effectively improved. Third, in the compounds of this invention, the presence of nitrogen atoms in rings A and B allows for effective coordination with n-type dopants, achieving efficient n-type doping and improving electron injection and transport performance.

[0124] Furthermore, in the compounds of the present invention, R1, R2, R3, R4, and R5 are preferably designed as electron-donating substituents, which can significantly enhance the electron cloud density and electrostatic potential near the nitrogen atom in structures such as bipyridine (ring A and ring B are connected by a single bond) or o-phenanthroline (ring A and ring B are both connected to ring P), which helps to improve their coordination ability with n-type dopants and achieve better electron injection and transport performance.

[0125] The combined synergistic effect of the innovative structural design of the compounds in this invention ensures that OLED devices prepared using these compounds possess numerous advantages, including low driving voltage, high device efficiency, and long lifespan, meeting the current requirements of OLED panel manufacturers for high-performance electron injection layer materials and interconnecting layers for stacked devices. Furthermore, the raw materials required for the preparation of these compounds are readily available, and the synthesis process, post-processing, and purification process are simple and reliable, making them suitable for both scientific research and industrial production. Attached Figure Description

[0126] Figure 1 This is a schematic diagram of the structure of the tandem organic electroluminescent device of the present invention. Detailed Implementation

[0127] The specific preparation methods of the above-mentioned new compounds of the present invention will be described in detail below using several synthetic examples, but the preparation methods of the present invention are not limited to these synthetic examples.

[0128] All the chemical reagents used in this invention, such as petroleum ether, dichloromethane, ethyl acetate, ethanol, toluene, sodium carbonate, and other basic chemical raw materials, were purchased from Shanghai Titan Technology Co., Ltd. The mass spectrometer used to determine the following compounds was a ZAB-HS type mass spectrometer (manufactured by Micromass, UK).

[0129] The synthetic method of the compounds described in this invention will be briefly described below. First, commercially available 4,7-dichloro-1,10-phenanthroline is used as the starting material. The 4,7 positions of o-phenanthroline are substituted and modified via Suzuki coupling (as shown in representative synthetic route 1). Subsequently, chlorination is performed at position 2 of the o-phenanthroline skeleton through multiple transformations. Finally, multiple o-phenanthroline skeletons are linked to bridging groups via Suzuki coupling to obtain the target product. For target products where the 4,7 positions of o-phenanthroline are directly bonded to heteroatoms (O, N, S, etc.), 4,7-dichloro-1,10-phenanthroline can be modified by base-catalyzed nucleophilic substitution (as shown in representative synthetic route 2), and the corresponding target product can be obtained through a similar process.

[0130] Synthesis Examples

[0131] Representative synthetic route 1:

[0132]

[0133] Representative synthetic route 2:

[0134]

[0135] More specifically, the following provides methods for synthesizing representative compounds of the present invention.

[0136] Synthesis Examples

[0137] Synthesis Example 1: Synthesis of Compound E-1

[0138]

[0139] E-1-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-1 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 672.85. Elemental analysis results: Theoretical values ​​(%): C, 87.48; H, 4.20; N, 8.33. Experimental values ​​(%): C, 87.49; H, 4.20; N, 8.32.

[0140] Synthesis Example 2: Synthesis of Compound E-6

[0141]

[0142] E-1-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-6 (70% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 89.73; H, 4.54; N, 5.73. Experimental values ​​(%): C, 89.75; H, 4.53; N, 5.72.

[0143] Synthesis Example 3: Synthesis of Compound E-7

[0144]

[0145] E-1-1 (8.48 mmol, 1 eq) and E-3-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-7 (71% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 1177.25. Elemental analysis results: Theoretical values ​​(%): C, 90.79; H, 4.45; N, 4.76. Experimental values ​​(%): C, 90.77; H, 4.45; N, 4.78.

[0146] Synthesis Example 4: Synthesis of Compound E-8

[0147]

[0148] E-1-1 (8.48 mmol, 1 eq) and E-4-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-8 (73% yield, HPLC purity 99.54%). MALDI-TOF-MS results: m / z: 1177.45. Elemental analysis results: Theoretical values ​​(%): C, 90.79; H, 4.45; N, 4.76. Experimental values ​​(%): C, 90.78; H, 4.46; N, 4.76.

[0149] Synthesis Example 5: Synthesis of Compound E-9

[0150]

[0151] E-1-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-9 (71% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 949.25. Elemental analysis results: Theoretical values ​​(%): C, 82.25; H, 5.95; N, 11.81. Experimental values ​​(%): C, 82.26; H, 5.94; N, 11.81.

[0152] Synthesis Example 6: Synthesis of Compound E-16

[0153]

[0154] E-1-1 (8.48 mmol, 1 eq) and E-6-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-16 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 1005.25. Elemental analysis results: Theoretical values ​​(%): C, 82.44; H, 6.41; N, 11.15. Experimental values ​​(%): C, 82.43; H, 6.41; N, 11.16.

[0155] Synthesis Example 7: Synthesis of Compound E-17

[0156]

[0157] E-1-1 (8.48 mmol, 1 eq) and E-7-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-17 (72% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 729.25. Elemental analysis results: Theoretical values ​​(%): C, 87.33; H, 4.98; N, 7.69. Experimental values ​​(%): C, 87.32; H, 4.99; N, 7.69.

[0158] Synthesis Example 8: Synthesis of Compound E-18

[0159]

[0160] E-1-1 (8.48 mmol, 1 eq) and E-8-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-18 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 793.05. Elemental analysis results: Theoretical values ​​(%): C, 80.29; H, 4.58; N, 7.07; O, 8.07. Experimental values ​​(%): C, 80.28; H, 4.58; N, 7.08; O, 8.07.

[0161] Synthesis Example 9: Synthesis of Compound E19-

[0162]

[0163] E-2-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-19 (72% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 672.85. Elemental analysis results: Theoretical values ​​(%): C, 87.48; H, 4.20; N, 8.32. Experimental values ​​(%): C, 87.47; H, 4.21; N, 8.32.

[0164] Synthesis Example 10: Synthesis of Compound E-24

[0165]

[0166] E-2-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-24 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 89.73; H, 4.54; N, 5.73. Experimental values ​​(%): C, 89.75; H, 4.53; N, 5.72.

[0167] Synthesis Example 11: Synthesis of Compound E-25

[0168]

[0169] E-2-1 (8.48 mmol, 1 eq) and E-3-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-25 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 1177.25. Elemental analysis results: Theoretical values ​​(%): C, 90.79; H, 4.45; N, 4.76. Experimental values ​​(%): C, 90.77; H, 4.47; N, 4.76.

[0170] Synthesis Example 12: Synthesis of Compound E-26

[0171]

[0172] E-2-1 (8.48 mmol, 1 eq) and E-4-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-26 (70% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 1177.25. Elemental analysis results: Theoretical values ​​(%): C, 90.79; H, 4.45; N, 4.76. Experimental values ​​(%): C, 90.77; H, 4.47; N, 4.76.

[0173] Synthesis Example 13: Synthesis of Compound E-27

[0174]

[0175] E-2-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-27 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 82.25; H, 5.95; N, 11.80. Experimental values ​​(%): C, 82.24; H, 5.95; N, 11.81.

[0176] Synthesis Example 14: Synthesis of Compound E-34

[0177]

[0178] E-2-1 (8.48 mmol, 1 eq) and E-6-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-34 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 1005.25. Elemental analysis results: Theoretical values ​​(%): C, 82.44; H, 6.42; N, 11.14. Experimental values ​​(%): C, 82.43; H, 6.42; N, 11.15.

[0179] Synthesis Example 15: Synthesis of Compound E-35

[0180]

[0181] E-2-1 (8.48 mmol, 1 eq) and E-7-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-36 (69% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 729.25. Elemental analysis results: Theoretical values ​​(%): C, 87.33; H, 4.98; N, 7.69. Experimental values ​​(%): C, 87.31; H, 4.98; N, 7.71.

[0182] Synthesis Example 16: Synthesis of Compound E-36

[0183]

[0184] E-2-1 (8.48 mmol, 1 eq) and E-8-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-36 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 793.25. Elemental analysis results: Theoretical values ​​(%): C, 80.29; H, 4.58; N, 7.07; O, 8.06. Experimental values ​​(%): C, 80.28; H, 4.58; N, 7.07; O, 8.07.

[0185] Synthesis Example 17: Synthesis of Compound E-37

[0186]

[0187] E-3-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-37 (72% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 689.25. Elemental analysis results: Theoretical values ​​(%): C, 83.69; H, 4.10; N, 8.13; Si, 4.08. Experimental values ​​(%): C, 83.68; H, 4.11; N, 8.13; Si, 4.08.

[0188] Synthesis Example 18: Synthesis of Compound E-42

[0189]

[0190] E-3-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-42 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 993.25. Elemental analysis results: Theoretical values ​​(%): C, 87.07; H, 4.47; N, 5.64; Si, 2.83. Experimental values ​​(%): C, 87.08; H, 4.47; N, 5.63; Si, 2.83.

[0191] Synthesis Example 19: Synthesis of Compound E-45

[0192]

[0193] E-3-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-45 (72% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 79.63; H, 5.85; N, 11.61; Si, 2.91. Experimental values ​​(%): C, 79.62; H, 5.85; N, 11.62; Si, 2.91.

[0194] Synthesis Example 20: Synthesis of Compound E-55

[0195]

[0196] E-4-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-55 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 689.25. Elemental analysis results: Theoretical values ​​(%): C, 83.69; H, 4.10; N, 8.13; Si, 4.08. Experimental values ​​(%): C, 83.68; H, 4.10; N, 8.14; Si, 4.08.

[0197] Synthesis Example 21: Synthesis of Compound E-60

[0198]

[0199] E-4-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-60 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 993.25. Elemental analysis results: Theoretical values ​​(%): C, 87.07; H, 4.47; N, 5.64; Si, 2.82. Experimental values ​​(%): C, 87.08; H, 4.46; N, 5.64; Si, 2.82.

[0200] Synthesis Example 22: Synthesis of Compound E-63

[0201]

[0202] E-4-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-63 (71% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 965.25. Elemental analysis results: Theoretical values ​​(%): C, 79.63; H, 5.85; N, 11.61; Si, 2.91. Experimental values ​​(%): C, 79.64; H, 5.85; N, 11.60; Si, 2.91.

[0203] Synthesis Example 23: Synthesis of Compound E-73

[0204]

[0205] E-5-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-73 (72% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 673.25. Elemental analysis results: Theoretical values ​​(%): C, 83.81; H, 4.19; B, 1.60; N, 10.40. Experimental values ​​(%): C, 83.80; H, 4.19; B, 1.60; N, 10.41.

[0206] Synthesis Example 24: Synthesis of Compound E-78

[0207]

[0208] E-5-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-78 (70% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 978.25. Elemental analysis results: Theoretical values ​​(%): C, 87.20; H, 4.54; B, 1.11; N, 7.16. Experimental values ​​(%): C, 87.21; H, 4.54; B, 1.11; N, 7.15.

[0209] Synthesis Example 25: Synthesis of Compound E-81

[0210]

[0211] E-5-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-81 (72% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 950.25. Elemental analysis results: Theoretical values ​​(%): C, 79.65; H, 5.94; B, 1.14; N, 13.27. Experimental values ​​(%): C, 79.66; H, 5.94; B, 1.14; N, 13.26.

[0212] Synthesis Example 26: Synthesis of Compound E-91

[0213]

[0214] E-6-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-91 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 83.81; H, 4.19; B, 1.60; N, 10.40. Experimental values ​​(%): C, 83.80; H, 4.20; B, 1.60; N, 10.40.

[0215] Synthesis Example 27: Synthesis of Compound E-96

[0216]

[0217] E-6-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-96 (72% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 978.25. Elemental analysis results: Theoretical values ​​(%): C, 87.20; H, 4.54; B, 1.11; N, 7.15. Experimental values ​​(%): C, 87.20; H, 4.53; B, 1.12; N, 7.15.

[0218] Synthesis Example 28: Synthesis of Compound E-99

[0219]

[0220] E-6-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-99 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 950.25. Elemental analysis results: Theoretical values ​​(%): C, 79.65; H, 5.94; B, 1.14; N, 13.27. Experimental values ​​(%): C, 79.65; H, 5.95; B, 1.13; N, 13.27.

[0221] Synthesis Example 29: Synthesis of Compound E-109

[0222]

[0223] E-1-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-109 (69% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 625.05. Elemental analysis results: Theoretical values ​​(%): C, 86.51; H, 4.52; N, 8.97. Experimental values ​​(%): C, 86.50; H, 4.53; N, 8.97.

[0224] Synthesis Example 30: Synthesis of Compound E-112

[0225]

[0226] E-1-1 (8.48 mmol, 1 eq) and E-10-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-112 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 88.12; H, 4.67; N, 7.21. Experimental values ​​(%): C, 88.12; H, 4.66; N, 7.22.

[0227] Synthesis Example 31: Synthesis of Compound E-115

[0228]

[0229] E-1-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-115 (68% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 901.25. Elemental analysis results: Theoretical values ​​(%): C, 81.31; H, 6.26; N, 12.43. Experimental values ​​(%): C, 81.32; H, 6.26; N, 12.42.

[0230] Synthesis Example 32: Synthesis of Compound E-125

[0231]

[0232] E-2-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-125 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 625.25. Elemental analysis results: Theoretical values ​​(%): C, 86.51; H, 4.52; N, 8.97. Experimental values ​​(%): C, 86.50; H, 4.52; N, 8.98.

[0233] Synthesis Example 33: Synthesis of Compound E-128

[0234]

[0235] E-2-1 (8.48 mmol, 1 eq) and E-10-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-128 (71% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 777.25. Elemental analysis results: Theoretical values ​​(%): C, 88.12; H, 4.67; N, 7.21. Experimental values ​​(%): C, 88.11; H, 4.67; N, 7.22.

[0236] Synthesis Example 34: Synthesis of Compound E-132

[0237]

[0238] E-2-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-132 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 901.25. Elemental analysis results: Theoretical values ​​(%): C, 81.30; H, 6.26; N, 12.44. Experimental values ​​(%): C, 81.30; H, 6.27; N, 12.43.

[0239] Synthesis Example 35: Synthesis of Compound E-142

[0240]

[0241] E-3-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-142 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 641.25. Elemental analysis results: Theoretical values ​​(%): C, 82.47; H, 4.40; N, 8.74; Si, 4.39. Experimental values ​​(%): C, 82.47; H, 4.41; N, 8.74; Si, 4.38.

[0242] Synthesis Example 36: Synthesis of Compound E-145

[0243]

[0244] E-3-1 (8.48 mmol, 1 eq) and E-10-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-145 (70% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 793.25. Elemental analysis results: Theoretical values ​​(%): C, 84.82; H, 4.58; N, 7.07; Si, 3.53. Experimental values ​​(%): C, 84.82; H, 4.58; N, 7.06; Si, 3.54.

[0245] Synthesis Example 37: Synthesis of Compound E-148

[0246]

[0247] E-3-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-148 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 917.25. Elemental analysis results: Theoretical values ​​(%): C, 78.57; H, 6.15; N, 12.22; Si, 3.06. Experimental values ​​(%): C, 78.58; H, 6.15; N, 12.21; Si, 3.06.

[0248] Synthesis Example 38: Synthesis of Compound E-158

[0249]

[0250] 3. In a 500 mL round-bottom flask, E-4-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-158 (70% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 641.25. Elemental analysis results: Theoretical values ​​(%): C, 82.47; H, 4.40; N, 8.75; Si, 4.38. Experimental values ​​(%): C, 82.47; H, 4.40; N, 8.74; Si, 4.39.

[0251] Synthesis Example 39: Synthesis of Compound E-162

[0252]

[0253] E-4-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-162 (71% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 945.25. Elemental analysis results: Theoretical values ​​(%): C, 86.41; H, 4.69; N, 5.93; Si, 2.97. Experimental values ​​(%): C, 86.42; H, 4.68; N, 5.93; Si, 2.97.

[0254] Synthesis Example 40: Synthesis of Compound E-165

[0255]

[0256] E-4-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-165 (69% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 917.25. Elemental analysis results: Theoretical values ​​(%): C, 78.57; H, 6.15; N, 12.22; Si, 3.06. Experimental values ​​(%): C, 78.58; H, 6.14; N, 12.22; Si, 3.06.

[0257] Synthesis Example 41: Synthesis of Compound E-175

[0258]

[0259] E-5-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-175 (67% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 625.25. Elemental analysis results: Theoretical values ​​(%): C, 82.56; H, 4.51; B, 1.73; N, 11.20. Experimental values ​​(%): C, 82.55; H, 4.52; B, 1.73; N, 11.20.

[0260] Synthesis Example 42: Synthesis of Compound E-179

[0261]

[0262] E-5-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-179 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 930.15. Elemental analysis results: Theoretical values ​​(%): C, 86.54; H, 4.77; B, 1.16; N, 7.53. Experimental values ​​(%): C, 86.55; H, 4.77; B, 1.16; N, 7.52.

[0263] Synthesis Example 43: Synthesis of Compound E-182

[0264]

[0265] E-5-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-182 (71% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 902.25. Elemental analysis results: Theoretical values ​​(%): C, 78.56; H, 6.26; B, 1.20; N, 13.98. Experimental values ​​(%): C, 78.57; H, 6.25; B, 1.20; N, 13.98.

[0266] Synthesis Example 44: Synthesis of Compound E-192

[0267]

[0268] E-6-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-192 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 625.25. Elemental analysis results: Theoretical values ​​(%): C, 82.56; H, 4.51; B, 1.73; N, 11.20. Experimental values ​​(%): C, 82.55; H, 4.52; B, 1.73; N, 11.20.

[0269] Synthesis Example 45: Synthesis of Compound E-196

[0270]

[0271] E-6-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-196 (72% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 86.54; H, 4.77; B, 1.16; N, 7.53. Experimental values ​​(%): C, 86.55; H, 4.77; B, 1.16; N, 7.52.

[0272] Synthesis Example 46: Synthesis of Compound E-199

[0273]

[0274] E-6-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-199 (70% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 902.25. Elemental analysis results: Theoretical values ​​(%): C, 78.56; H, 6.26; B, 1.20; N, 13.98. Experimental values ​​(%): C, 78.55; H, 6.27; B, 1.20; N, 13.98.

[0275] Synthesis Example 47: Synthesis of Compound E-209

[0276]

[0277] E-7-1 (8.48 mmol, 1 eq) and E-1-2 (29.68 mmol, 3.5 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (101.76 mmol, 12 eq) and Pd(PPh₃)₄ (2.12 mmol, 0.25 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-209 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 851.25. Elemental analysis results: Theoretical values ​​(%): C, 86.10; H, 4.02; N, 9.88. Experimental values ​​(%): C, 86.11; H, 4.01; N, 9.88.

[0278] Synthesis Example 48: Synthesis of Compound E-279

[0279]

[0280] E-8-1 (8.48 mmol, 1 eq) and E-1-2 (38.16 mmol, 4.5 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (135.68 mmol, 16 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-279 (61% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 1029.25. Elemental analysis results: Theoretical values ​​(%): C, 85.19; H, 3.92; N, 10.89. Experimental values ​​(%): C, 85.20; H, 3.91; N, 10.89.

[0281] Synthesis Example 49: Synthesis of Compound E-349

[0282]

[0283] E-9-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-349 (68% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 677.25. Elemental analysis results: Theoretical values ​​(%): C, 86.96; H, 4.76; N, 8.28. Experimental values ​​(%): C, 86.95; H, 4.77; N, 8.28.

[0284] Synthesis Example 50: Synthesis of Compound E-354

[0285]

[0286] E-9-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-354 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 981.25. Elemental analysis results: Theoretical values ​​(%): C, 89.36; H, 4.93; N, 5.71. Experimental values ​​(%): C, 89.36; H, 4.92; N, 5.72.

[0287] Synthesis Example 51: Synthesis of Compound E-357

[0288]

[0289] E-9-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-357 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 953.25. Elemental analysis results: Theoretical values ​​(%): C, 81.90; H, 6.34; N, 11.76. Experimental values ​​(%): C, 81.90; H, 6.33; N, 11.77.

[0290] Synthesis Example 52: Synthesis of Compound E-421

[0291]

[0292] E-9-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-421 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 629.25. Elemental analysis results: Theoretical values ​​(%): C, 85.96; H, 5.13; N, 8.91. Experimental values ​​(%): C, 85.97; H, 5.13; N, 8.90.

[0293] Synthesis Example 53: Synthesis of Compound E-424

[0294]

[0295] E-9-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-424 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 781.05. Elemental analysis results: Theoretical values ​​(%): C, 87.67; H, 5.16; N, 7.17. Experimental values ​​(%): C, 87.66; H, 5.17; N, 7.17.

[0296] Synthesis Example 54: Synthesis of Compound E-427

[0297]

[0298] E-9-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-427 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 905.25. Elemental analysis results: Theoretical values ​​(%): C, 80.94; H, 6.68; N, 12.38. Experimental values ​​(%): C, 80.94; H, 6.69; N, 12.37.

[0299] Synthesis Example 55: Synthesis of Compound E-626

[0300]

[0301] E-10-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-626 (65% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 673.25. Elemental analysis results: Theoretical values ​​(%): C, 87.48; H, 4.20; N, 8.32. Experimental values ​​(%): C, 87.47; H, 4.20; N, 8.33.

[0302] Synthesis Example 56: Synthesis of Compound E-631

[0303]

[0304] E-10-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-631 (72% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 977.25. Elemental analysis results: Theoretical values ​​(%): C, 89.73; H, 4.54; N, 5.73. Experimental values ​​(%): C, 89.74; H, 4.54; N, 5.72.

[0305] Synthesis Example 57: Synthesis of Compound E-634

[0306]

[0307] E-10-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-634 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 949.25. Elemental analysis results: Theoretical values ​​(%): C, 82.25; H, 5.95; N, 11.80. Experimental values ​​(%): C, 82.24; H, 5.95; N, 11.81.

[0308] Synthesis Example 58: Synthesis of Compound E-644

[0309]

[0310] E-11-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-644 (64% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 677.25. Elemental analysis results: Theoretical values ​​(%): C, 86.96; H, 4.76; N, 8.28. Experimental values ​​(%): C, 86.95; H, 4.77; N, 8.28.

[0311] Synthesis Example 59: Synthesis of Compound E-649

[0312]

[0313] E-11-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-649 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 981.25. Elemental analysis results: Theoretical values ​​(%): C, 89.36; H, 4.93; N, 5.71. Experimental values ​​(%): C, 89.37; H, 4.93; N, 5.70.

[0314] Synthesis Example 60: Synthesis of Compound E-652

[0315]

[0316] E-11-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-652 (62% yield, HPLC purity 99.66%). MALDI-TOF-MS results: m / z: 953.25. Elemental analysis results: Theoretical values ​​(%): C, 81.90; H, 6.34; N, 11.76. Experimental values ​​(%): C, 81.90; H, 6.35; N, 11.75.

[0317] Synthesis Example 61: Synthesis of Compound E-662

[0318]

[0319] E-12-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-662 (63% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 689.25. Elemental analysis results: Theoretical values ​​(%): C, 83.69; H, 4.10; N, 8.13; Si, 4.08. Experimental values ​​(%): C, 83.67; H, 4.10; N, 8.15; Si, 4.08.

[0320] Synthesis Example 62: Synthesis of Compound E-667

[0321]

[0322] E-12-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-667 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 993.25. Elemental analysis results: Theoretical values ​​(%): C, 87.07; H, 4.47; N, 5.64; Si, 2.82. Experimental values ​​(%): C, 87.07; H, 4.47; N, 5.63; Si, 2.83.

[0323] Synthesis Example 63: Synthesis of Compound E-670

[0324]

[0325] E-12-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-670 (60% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 965.25. Elemental analysis results: Theoretical values ​​(%): C, 79.63; H, 5.85; N, 11.61; Si, 2.91. Experimental values ​​(%): C, 79.63; H, 5.84; N, 11.62; Si, 2.91.

[0326] Synthesis Example 64: Synthesis of Compound E-680

[0327]

[0328] E-13-1 (8.48 mmol, 1 eq) and E-1-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-680 (63% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 693.25. Elemental analysis results: Theoretical values ​​(%): C, 83.20; H, 4.66; N, 8.09; Si, 4.05. Experimental values ​​(%): C, 83.21; H, 4.66; N, 8.09; Si, 4.04.

[0329] Synthesis Example 65: Synthesis of Compound E-685

[0330]

[0331] E-13-1 (8.48 mmol, 1 eq) and E-2-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-685 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 997.25. Elemental analysis results: Theoretical values ​​(%): C, 86.71; H, 4.85; N, 5.62; Si, 2.82. Experimental values ​​(%): C, 86.72; H, 4.84; N, 5.62; Si, 2.82.

[0332] Synthesis Example 66: Synthesis of Compound E-688

[0333]

[0334] E-13-1 (8.48 mmol, 1 eq) and E-5-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-688 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 969.25. Elemental analysis results: Theoretical values ​​(%): C, 79.30; H, 6.24; N, 11.56; Si, 2.90. Experimental values ​​(%): C, 79.30; H, 6.25; N, 11.55; Si, 2.90.

[0335] Synthesis Example 67: Synthesis of Compound E-698

[0336]

[0337] E-10-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-698 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 624.85. Elemental analysis results: Theoretical values ​​(%): C, 86.51; H, 4.52; N, 8.97. Experimental values ​​(%): C, 86.52; H, 4.52; N, 8.96.

[0338] Synthesis Example 68: Synthesis of Compound E-702

[0339]

[0340] E-10-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-702 (62% yield, HPLC purity 99.46%). MALDI-TOF-MS results: m / z: 929.25. Elemental analysis results: Theoretical values ​​(%): C, 89.20; H, 4.77; N, 6.03. Experimental values ​​(%): C, 89.20; H, 4.76; N, 6.04.

[0341] Synthesis Example 69: Synthesis of Compound E-705

[0342]

[0343] E-10-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-705 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 901.25. Elemental analysis results: Theoretical values ​​(%): C, 81.30; H, 6.27; N, 12.43. Experimental values ​​(%): C, 81.30; H, 6.26; N, 12.44.

[0344] Synthesis Example 70: Synthesis of Compound E-715

[0345]

[0346] E-11-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-715 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 629.25. Elemental analysis results: Theoretical values ​​(%): C, 85.96; H, 5.13; N, 8.91. Experimental values ​​(%): C, 85.96; H, 5.14; N, 8.90.

[0347] Synthesis Example 71: Synthesis of Compound E-719

[0348]

[0349] E-11-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-719 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 933.25. Elemental analysis results: Theoretical values ​​(%): C, 88.81; H, 5.18; N, 6.00. Experimental values ​​(%): C, 88.81; H, 5.18; N, 6.00.

[0350] Synthesis Example 72: Synthesis of Compound E-722

[0351]

[0352] E-11-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-722 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 905.25. Elemental analysis results: Theoretical values ​​(%): C, 80.94; H, 6.68; N, 12.38. Experimental values ​​(%): C, 80.92; H, 6.69; N, 12.39.

[0353] Synthesis Example 73: Synthesis of Compound E-732

[0354]

[0355] E-12-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-732 (60% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 641.25. Elemental analysis results: Theoretical values ​​(%): C, 82.47; H, 4.40; N, 8.75; Si, 4.38. Experimental values ​​(%): C, 82.48; H, 4.40; N, 8.74; Si, 4.38.

[0356] Synthesis Example 74: Synthesis of Compound E-736

[0357]

[0358] E-12-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-736 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 945.25. Elemental analysis results: Theoretical values ​​(%): C, 86.41; H, 4.69; N, 5.93; Si, 2.97. Experimental values ​​(%): C, 86.41; H, 4.69; N, 5.92; Si, 2.98.

[0359] Synthesis Example 75: Synthesis of Compound E-739

[0360]

[0361] E-12-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-739 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 917.25. Elemental analysis results: Theoretical values ​​(%): C, 78.57; H, 6.15; N, 12.22; Si, 3.06. Experimental values ​​(%): C, 78.58; H, 6.14; N, 12.22; Si, 3.06.

[0362] Synthesis Example 76: Synthesis of Compound E-749

[0363]

[0364] E-13-1 (8.48 mmol, 1 eq) and E-9-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-749 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 645.25. Elemental analysis results: Theoretical values ​​(%): C, 81.95; H, 5.00; N, 8.69; Si, 4.36. Experimental values ​​(%): C, 81.94; H, 5.00; N, 8.69; Si, 4.37.

[0365] Synthesis Example 77: Synthesis of Compound E-753

[0366]

[0367] E-13-1 (8.48 mmol, 1 eq) and E-12-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-753 (61% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 949.25. Elemental analysis results: Theoretical values ​​(%): C, 86.04; H, 5.10; N, 5.90; Si, 2.96. Experimental values ​​(%): C, 86.05; H, 5.10; N, 5.90; Si, 2.95.

[0368] Synthesis Example 78: Synthesis of Compound E-756

[0369]

[0370] E-13-1 (8.48 mmol, 1 eq) and E-11-2 (19.08 mmol, 2.25 eq) were added to a 500 mL round-bottom flask. A mixture of toluene (160 mL), ethanol (60 mL), and deionized water (100 mL) was used as the solvent. Na₂CO₃ (67.84 mmol, 8 eq) and Pd(PPh₃)₄ (1.27 mmol, 0.15 eq) were added as catalysts. The mixture was heated under reflux for 36 hours under nitrogen protection. After cooling, the mixture was filtered, and the filter cake was washed successively with saturated brine and ethanol. Further processing using conventional methods yielded the final product E-756 (62% yield, HPLC purity 99.56%). MALDI-TOF-MS results: m / z: 921.25. Elemental analysis results: Theoretical values ​​(%): C, 78.22; H, 6.56; N, 12.16; Si, 3.06. Experimental values ​​(%): C, 78.22; H, 6.56; N, 12.17; Si, 3.05.

[0371] The following section demonstrates the technical features and advantages of this invention by applying the organic materials of this invention to single-junction OLED devices and tandem OLED devices, respectively, and by testing the performance of the devices.

[0372] Fabrication of single-junction OLED devices:

[0373] Application examples of the compounds of this invention, namely, examples of preparing single-junction OLED devices.

[0374] An OLED includes a first electrode and a second electrode, and an organic material layer located between the electrodes. This organic material layer can be further divided into multiple regions. For example, the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0375] In specific embodiments, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, thin-film transistors (TFTs) can also be incorporated into the substrate used for displays.

[0376] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0377] Organic material layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic material layers can be small organic molecules, large organic molecules, polymers, and combinations thereof.

[0378] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0379] The material for the hole transport region can be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives, etc.

[0380] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds.

[0381] The emissive layer includes luminescent dyes (i.e., dopants) that can emit different wavelengths of light, and may also include a host material. The emissive layer can be a monochromatic emissive layer emitting a single color such as red, green, or blue. Multiple monochromatic emissive layers of different colors can be arranged in a planar pattern according to pixel design, or they can be stacked together to form a colored emissive layer. When different colored emissive layers are stacked together, they can be separated from each other or connected to each other. The emissive layer can also be a single colored emissive layer that can simultaneously emit different colors such as red, green, and blue.

[0382] Depending on the technology used, the light-emitting layer material can be various, including fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescence materials. An OLED device can employ a single light-emitting technology or a combination of different technologies. These different light-emitting materials, categorized by technology, can emit light of the same color or different colors.

[0383] The OLED organic material layer may also include an electron transport region between the light-emitting layer and the cathode. The electron transport region can be a single-layer electron transport layer (ETL), including single-layer electron transport layers containing only one compound and single-layer electron transport layers containing multiple compounds. Alternatively, the electron transport region can be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0384] The electron injection layer in this invention employs an n-type dopant and the o-phenanthroline-based electron injection material described herein. The n-type dopant is primarily composed of alkali metals, alkaline earth metals, and some transition metals and their salts, including but not limited to one or a mixture of several of lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), magnesium (Mg), calcium (Ca), iron (Fe), chromium (Cr), niobium (Nb), cobalt (Co), manganese (Mn), nickel (Ni), copper (Cu), zinc (Zn), silver (Ag), palladium (Pd), rhodium (Rh), ruthenium (Ru), iridium (Ir), tungsten (W), rhenium (Re), platinum (Pt), gold (Au), and ytterbium (Yb). The doping ratio of the metallic n-type dopant in the electron injection layer is from 0.1 wt% to 50 wt%, corresponding to a doping ratio of 0.01 vol% to 5 vol%, with a preferred doping ratio of 0.05 wt% to 20 wt%. Its total thickness ranges from 0.1 nm to 20 nm, more preferably 3-5 nm.

[0385] The fabrication process of the single-junction organic electroluminescent device in this embodiment is as follows:

[0386] The glass plate coated with the ITO transparent conductive layer was ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in a acetone:ethanol mixed solvent, baked in a clean environment until all moisture was removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam.

[0387] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5 ~5×10 -4 Pa, HATCN was vacuum-deposited as a hole injection layer on the above-mentioned anodic layer film at a deposition rate of 0.05 nm / s and a film thickness of 5 nm.

[0388] NPB was vacuum-deposited on top of the hole injection layer as the hole transport layer of the device at a deposition rate of 0.1 nm / s and a total film thickness of 30 nm.

[0389] An electron blocking layer and a light-emitting layer of a device are vacuum-deposited on top of a hole transport layer. The light-emitting layer of this invention includes a host material and a dye material, and is doped using a multi-source co-evaporation method. The deposition rate and doping concentration are controlled by high and low crystal oscillator probes. The deposition rate of the host material is adjusted to 0.1 nm / s, and the deposition rate of the dye in the light-emitting layer is adjusted to 1%-5% of the deposition rate of the host material, thereby achieving a predetermined doping ratio. The total film thickness of the light-emitting layer is 20-50 nm.

[0390] Hole blocking layer and electron transport layer materials of the device are vacuum-deposited on the light-emitting layer at a deposition rate of 0.1 nm / s and a total film thickness of 20-60 nm.

[0391] Electron injection layers are formed by simultaneously depositing metallic Ag and o-phenanthroline compounds of this invention on the electron transport layer (ETL). In-situ doping is achieved by adjusting the deposition rates of the respective materials, wherein the deposition rate ratio of metallic Ag to organic material is 1%-10% (i.e., the volume fraction is 0.1 vol%-1 vol%), and the total thickness of the electron injection layer is controlled to be 5 nm.

[0392] Finally, 150 nm of Al was vacuum-deposited onto the electron injection layer to serve as the cathode of the device.

[0393]

[0394]

[0395] Device Example 1

[0396] In this embodiment, a 5nm Ag:E-1 layer (with a deposition rate ratio of 3%) is used as the electron injection layer, and a 150nm Al layer is used as the cathode of the device. This results in the following structure:

[0397] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-1(5nm) / Al(150nm).

[0398] Device Example 2

[0399] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-6 instead of E-1, and the Ag:E-6 evaporation rate ratio is 3%. The device structure is as follows:

[0400] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-6(5nm) / Al(150nm).

[0401] Device Example 3

[0402] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-7 instead of E-1, and the Ag:E-7 evaporation rate ratio is 3%. The device structure is as follows:

[0403] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-7(5nm) / Al(150nm).

[0404] Device Example 4

[0405] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-8 instead of E-1, and the Ag:E-8 evaporation rate ratio is 3%. The device structure is as follows:

[0406] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-8(5nm) / Al(150nm).

[0407] Device Example 5

[0408] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-9 instead of E-1, and the Ag:E-9 evaporation rate ratio is 3%. The device structure is as follows:

[0409] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-9(5nm) / Al(150nm).

[0410] Device Example 6

[0411] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-16 instead of E-16, and the Ag:E-16 evaporation rate ratio is 3%. The device structure is as follows:

[0412] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-16(5nm) / Al(150nm).

[0413] Device Example 7

[0414] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-17 instead of E-17, and the Ag:E-17 evaporation rate ratio is 3%. The device structure is as follows:

[0415] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-17(5nm) / Al(150nm).

[0416] Device Example 8

[0417] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-18, and the Ag:E-18 evaporation rate ratio is 3%. The device structure is as follows:

[0418] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-18(5nm) / Al(150nm).

[0419] Device Example 9

[0420] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-19, and the Ag:E-19 evaporation rate ratio is 3%. The device structure is as follows:

[0421] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-19(5nm) / Al(150nm).

[0422] Device Example 10

[0423] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-37 instead of E-1, and the Ag:E-37 evaporation rate ratio is 3%. The device structure is as follows:

[0424] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-37(5nm) / Al(150nm).

[0425] Device Example 11

[0426] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-42 instead of E-1, and the Ag:E-42 deposition rate ratio is 3%. The device structure is as follows:

[0427] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-42(5nm) / Al(150nm).

[0428] Device Example 12

[0429] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-45 instead of E-1, and the Ag:E-45 deposition rate ratio is 3%. The device structure is as follows:

[0430] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-45(5nm) / Al(150nm).

[0431] Device Example 13

[0432] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-55 instead of E-1, and the Ag:E-55 evaporation rate ratio is 3%. The device structure is as follows:

[0433] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-55(5nm) / Al(150nm).

[0434] Device Example 14

[0435] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-73 instead of E-1, and the Ag:E-73 evaporation rate ratio is 3%. The device structure is as follows:

[0436] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-73(5nm) / Al(150nm).

[0437] Device Example 15

[0438] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-91 instead of E-1, and the Ag:E-91 evaporation rate ratio is 3%. The device structure is as follows:

[0439] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-91(5nm) / Al(150nm).

[0440] Device Example 16

[0441] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-109 instead of E-1, and the Ag:E-109 evaporation rate ratio is 3%. The device structure is as follows:

[0442] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-109(5nm) / Al(150nm).

[0443] Device Example 17

[0444] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-115, and the Ag:E-115 evaporation rate ratio is 3%. The device structure is as follows:

[0445] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-115(5nm) / Al(150nm).

[0446] Device Example 18

[0447] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-125, and the Ag:E-125 evaporation rate ratio is 3%. The device structure is as follows:

[0448] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-125(5nm) / Al(150nm).

[0449] Device Example 19

[0450] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-142, and the Ag:E-142 evaporation rate ratio is 3%. The device structure is as follows:

[0451] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-142(5nm) / Al(150nm).

[0452] Device Example 20

[0453] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-148, and the Ag:E-148 evaporation rate ratio is 3%. The device structure is as follows:

[0454] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-148(5nm) / Al(150nm).

[0455] Device Example 21

[0456] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-158, and the Ag:E-158 evaporation rate ratio is 3%. The device structure is as follows:

[0457] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-158(5nm) / Al(150nm).

[0458] Device Example 22

[0459] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-175 instead of E-1, and the Ag:E-175 evaporation rate ratio is 3%. The device structure is as follows:

[0460] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-175(5nm) / Al(150nm).

[0461] Device Example 23

[0462] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-192, and the Ag:E-192 deposition rate ratio is 3%. The device structure is as follows:

[0463] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-192(5nm) / Al(150nm).

[0464] Device Example 24

[0465] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-209 instead of E-1, and the Ag:E-209 evaporation rate ratio is 3%. The device structure is as follows:

[0466] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-209(5nm) / Al(150nm).

[0467] Device Example 25

[0468] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-279 instead of E-1, and the Ag:E-279 evaporation rate ratio is 3%. The device structure is as follows:

[0469] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-279(5nm) / Al(150nm).

[0470] Device Example 26

[0471] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-349 instead of E-1, and the Ag:E-349 evaporation rate ratio is 3%. The device structure is as follows:

[0472] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-349(5nm) / Al(150nm).

[0473] Device Example 27

[0474] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-357 instead of E-1, and the Ag:E-357 evaporation rate ratio is 3%. The device structure is as follows:

[0475] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-357(5nm) / Al(150nm).

[0476] Device Example 28

[0477] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-421 instead of E-1, and the Ag:E-421 evaporation rate ratio is 3%. The device structure is as follows:

[0478] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-421(5nm) / Al(150nm).

[0479] Device Example 29

[0480] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-427 instead of E-1, and the Ag:E-427 deposition rate ratio is 3%. The device structure is as follows:

[0481] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-427(5nm) / Al(150nm).

[0482] Device Example 30

[0483] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-626 instead of E-1, and the Ag:E-626 evaporation rate ratio is 3%. The device structure is as follows:

[0484] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-626(5nm) / Al(150nm).

[0485] Device Example 31

[0486] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-631 instead of E-1, and the Ag:E-631 deposition rate ratio is 3%. The device structure is as follows:

[0487] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-631(5nm) / Al(150nm).

[0488] Device Example 32

[0489] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-634 instead of E-1, and the Ag:E-634 evaporation rate ratio is 3%. The device structure is as follows:

[0490] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-634(5nm) / Al(150nm).

[0491] Device Example 33

[0492] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-644 instead of E-1, and the Ag:E-644 evaporation rate ratio is 3%. The device structure is as follows:

[0493] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-644(5nm) / Al(150nm).

[0494] Device Example 34

[0495] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-652 instead of E-1, and the Ag:E-652 deposition rate ratio is 3%. The device structure is as follows:

[0496] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-652(5nm) / Al(150nm).

[0497] Device Example 35

[0498] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-662 instead of E-1, and the Ag:E-662 deposition rate ratio is 3%. The device structure is as follows:

[0499] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-662(5nm) / Al(150nm).

[0500] Device Example 36

[0501] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-667 instead of E-1, and the Ag:E-667 evaporation rate ratio is 3%. The device structure is as follows:

[0502] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-667(5nm) / Al(150nm).

[0503] Device Example 37

[0504] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-670 instead of E-1, and the Ag:E-670 deposition rate ratio is 3%. The device structure is as follows:

[0505] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-670(5nm) / Al(150nm).

[0506] Device Example 38

[0507] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-680 instead of E-1, and the Ag:E-680 deposition rate ratio is 3%. The device structure is as follows:

[0508] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-680(5nm) / Al(150nm).

[0509] Device Example 39

[0510] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-698 instead of E-1, and the Ag:E-698 evaporation rate ratio is 3%. The device structure is as follows:

[0511] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-698(5nm) / Al(150nm).

[0512] Device Example 40

[0513] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-705 instead of E-1, and the Ag:E-705 deposition rate ratio is 3%. The device structure is as follows:

[0514] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-705(5nm) / Al(150nm).

[0515] Device Example 41

[0516] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-715, and the Ag:E-715 evaporation rate ratio is 3%. The device structure is as follows:

[0517] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-715(5nm) / Al(150nm).

[0518] Device Example 42

[0519] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-722 instead of E-1, and the Ag:E-722 deposition rate ratio is 3%. The device structure is as follows:

[0520] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-722(5nm) / Al(150nm).

[0521] Device Example 43

[0522] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-732 instead of E-1, and the Ag:E-732 evaporation rate ratio is 3%. The device structure is as follows:

[0523] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-732(5nm) / Al(150nm).

[0524] Device Example 44

[0525] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-739 instead of E-1, and the Ag:E-739 deposition rate ratio is 3%. The device structure is as follows:

[0526] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-739(5nm) / Al(150nm).

[0527] Device Example 45

[0528] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with E-749 instead of E-1, and the Ag:E-749 evaporation rate ratio is 3%. The device structure is as follows:

[0529] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:E-749(5nm) / Al(150nm).

[0530] Device Example 46

[0531] The preparation method is the same as in Example 1, except that the doping metal is replaced with Yb instead of Ag, and the Yb:E-1 evaporation rate ratio is 3%. The device structure is as follows:

[0532] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Yb:E-1(5nm) / Al(150nm).

[0533] Device Example 47

[0534] The preparation method is the same as in Example 1, except that the doping metal is replaced with Zn instead of Ag, and the Zn:E-1 evaporation rate ratio is 3%. The device structure is as follows:

[0535] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Zn:E-1(5nm) / Al(150nm).

[0536] Device Example 48

[0537] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with Yb:E-9 instead of Ag:E-1, and the Yb:E-9 evaporation rate ratio is 3%. The device structure is as follows:

[0538] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Yb:E-9(5nm) / Al(150nm).

[0539] Device Example 49

[0540] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with Zn:E-9 instead of Ag:E-1, and the Zn:E-9 evaporation rate ratio is 3%. The device structure is as follows:

[0541] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Zn:E-9(5nm) / Al(150nm).

[0542] Device Example 50

[0543] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with Yb:E-626 instead of Ag:E-1, and the Yb:E-626 evaporation rate is 3%. The device structure is as follows:

[0544] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Yb:E-626(5nm) / Al(150nm).

[0545] Device Example 51

[0546] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with Zn:E-626 instead of Ag:E-1, and the Zn:E-626 evaporation rate is 3%. The device structure is as follows:

[0547] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Zn:E-626(5nm) / Al(150nm).

[0548] Device Example 52

[0549] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with Yb:E-634 instead of Ag:E-1, and the Yb:E-634 evaporation rate is 3%. The device structure is as follows:

[0550] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Yb:E-634(5nm) / Al(150nm).

[0551] Device Example 53

[0552] The preparation method is the same as in Example 1, except that the electron injection layer material is replaced with Zn:E-634 instead of Ag:E-1, and the Zn:E-634 evaporation rate is 3%. The device structure is as follows:

[0553] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Zn:E-634(5nm) / Al(150nm).

[0554] Comparative Device Example 1

[0555] The preparation method is the same as in Example 1, except that the electron injection material is replaced by the existing compound Cs2CO3 instead of Ag:E-1. That is, the electron injection layer uses Cs2CO3:E-1 (5nm) with a evaporation rate ratio of 10% for Cs2CO3:E-1.

[0556] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%, 30nm) / HBL(10nm) / DPPyA(20nm) / Cs2CO3:E-1(10%, 5nm) / Al(150nm).

[0557] Comparative Device Example 2

[0558] The preparation method is the same as in Example 1, except that the electron injection layer is replaced by the prior art compound LiF (1 nm) instead of Ag:E-1 (5 nm).

[0559] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / LiF(1nm) / Al(150nm).

[0560] Comparative Device Example 3

[0561] The preparation method is the same as in Example 1, except that the electron injection layer is replaced by the prior art compound Liq (1 nm) instead of Ag:E-1 (5 nm).

[0562] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Liq(1nm) / Al(150nm).

[0563] Comparative Device Example 4

[0564] The preparation method is the same as in Example 1, except that the electron injection layer is replaced with the prior art compound Ag:D-1 instead of Ag:E-1 (5nm). The Ag:D-1 evaporation rate is 10%. The device structure is as follows:

[0565] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:D-1(5nm) / Al(150nm).

[0566] Comparative Device Example 5

[0567] The preparation method is the same as in Example 1, except that the electron injection layer is replaced with compound D-2 from the prior art instead of Ag:E-1 (5nm). The Ag:D-2 deposition rate ratio is 10%, and the thickness is 5nm. The device structure is as follows:

[0568] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Ag:D-2(5nm) / Al(150nm).

[0569] Comparative Device Example 6

[0570] The preparation method is the same as in Example 1, except that the electron injection layer is replaced with the prior art compound Yb:D-2 instead of Ag:E-1 (5nm). The Yb:D-2 deposition rate is 10%. The device structure is as follows:

[0571] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Yb:D-2(5nm) / Al(150nm).

[0572] Comparative Device Example 7

[0573] The preparation method is the same as in Example 1, except that the electron injection layer is replaced with the prior art compound Zn:D-2 instead of Ag:E-1 (5nm). The Zn:D-2 deposition rate is 10%. The device structure is as follows:

[0574] ITO / HATCN(5nm) / NPB(30nm) / EBL(10nm) / t-DABNA:α,β-ADN(2%,30nm) / HBL(10nm) / DPPyA(20nm) / Zn:D-2(5nm) / Al(150nm).

[0575] The performance of the organic electroluminescent devices prepared in the above-mentioned device embodiments and comparative device embodiments is shown in Table 1 below.

[0576] Table 1:

[0577]

[0578]

[0579] As shown in Table 1, through Examples 5, 6, 8, 46, and 47 and Comparative Examples 1 to 3, it can be observed that, with other materials remaining the same in the organic electroluminescent device structure, the OLED devices prepared by the compounds of the present invention exhibit lower voltages compared to the prior art compounds in Comparative Examples 1 to 3, while the device efficiency is significantly improved, and the device lifetime is correspondingly increased. It is speculated that when using alkali metal compounds as implantation materials, alkali metal ions may migrate or diffuse during heating and evaporation and during device operation, leading to exciton quenching in the light-emitting layer, thus causing a decrease in efficiency and lifetime. However, transition metal n-type dopants such as Ag have strong interactions with o-phenanthroline organic ligands, which helps to suppress metal migration or diffusion. Furthermore, the electron injection layer prepared based on the transition metal coordination doping strategy has better implantation performance, thus contributing to improved exciton utilization and the efficiency and lifetime of the OLED device.

[0580] The prior art compound D1 used in Comparative Example 4 is 4,7-diphenyl-o-phenanthroline (Bphen), a commonly used electron transport material. It has excellent coordination properties and can be used as a highly efficient electron injection layer in existing technologies after Ag doping. However, this compound has a molecular weight of only 332.41, resulting in a glass transition temperature of only 62℃ and poor film stability, thus leading to a relatively low lifetime in Comparative Example 4.

[0581] The prior art compound D2 used in Comparative Example 5 is a commonly used electron transport material. A comparison with Example 1 using compound E-1 of this invention reveals that E1, by replacing the benzene ring as the bridging group with a spirofluorene group that exhibits stronger transport performance, is more conducive to electron transport. The electron injection performance of electron injection layers using Ag:E1, Yb:E1, and Zn:E1 as electron injection layer materials is significantly better than that of electron injection layers composed of Ag:D2, Yb:D2, and Zn:D2. Compared to D2, devices using E1 as the organic ligand have lower driving voltages, higher current efficiency, and improved device lifetime. Further comparisons of Examples 1 and 2 to 8 show that, with consistent backbone groups, the stronger the electron-donating properties of R1 and R2, the stronger the coordination properties of the corresponding phenanthroline ligand, resulting in better performance of the prepared electron injection layer. This significantly reduces the device driving voltage and improves device efficiency and lifetime. This also reflects that the selection of R1 and R2 in the core structure of the compound of the present invention has an important influence on the performance of this type of phenanthroline material when paired with a transition metal as an electron injection layer.

[0582] In summary, the poly-n-phenanthroline-based electron injection materials described in this invention have a large molecular weight and exhibit good thin-film stability after doping with n-type dopants such as Ag, Yb, and Zn. Their coordination properties can be controlled by optimizing the molecular structure design. When combined with n-type dopants such as Ag, Yb, and Zn as an electron injection layer, they can achieve a low work function and excellent electron injection performance, thus enabling their application in OLED devices to simultaneously achieve high efficiency and long lifetime.

[0583] Fabrication of tandem OLED devices:

[0584] The following section demonstrates and verifies the technical features and advantages of this invention by showcasing the practical application of the connecting layer described in this invention in a tandem organic electroluminescent device and by testing the device's performance.

[0585] A tandem OLED device includes an anode, a cathode, and an organic material layer located between the two electrodes. This organic material layer can be further divided into multiple regions. For example, the organic material layer may include a hole transport region, a light-emitting layer, and an electron transport region.

[0586] In specific embodiments, a substrate can be used below the first electrode or above the second electrode. The substrate is typically made of glass or polymer material with excellent mechanical strength, thermal stability, water resistance, and transparency. Furthermore, thin-film transistors (TFTs) can also be incorporated into the substrate used for displays.

[0587] The first electrode can be formed by sputtering or depositing the material to be used as the first electrode on a substrate. When the first electrode is used as the anode, transparent conductive oxide materials such as indium tin oxide (ITO), indium zinc oxide (IZO), tin dioxide (SnO2), and zinc oxide (ZnO) and any combination thereof can be used. When the first electrode is used as the cathode, metals or alloys such as magnesium (Mg), silver (Ag), aluminum (Al), aluminum-lithium (Al-Li), calcium (Ca), magnesium-indium (Mg-In), and magnesium-silver (Mg-Ag) and any combination thereof can be used.

[0588] Organic material layers can be formed on electrodes using methods such as vacuum thermal evaporation, spin coating, and printing. The compounds used as organic material layers can be small organic molecules, large organic molecules, polymers, and combinations thereof.

[0589] The hole transport region is located between the anode and the light-emitting layer. The hole transport region can be a single-layer hole transport layer (HTL), including a single-layer hole transport layer containing only one compound and a single-layer hole transport layer containing multiple compounds. The hole transport region can also be a multilayer structure including at least one of a hole injection layer (HIL), a hole transport layer (HTL), and an electron blocking layer (EBL).

[0590] The material for the hole transport region can be selected from, but is not limited to, phthalocyanine derivatives such as CuPc, conductive polymers or polymers containing conductive dopants such as polyphenylene ethylene, polyaniline / dodecylbenzenesulfonic acid (Pani / DBSA), poly(3,4-ethylenedioxythiophene) / poly(4-styrenesulfonate) (PEDOT / PSS), polyaniline / camphorsulfonic acid (Pani / CSA), polyaniline / poly(4-styrenesulfonate) (Pani / PSS), aromatic amine derivatives, etc.

[0591] The hole injection layer is located between the anode and the hole transport layer. The hole injection layer can be a single compound material or a combination of multiple compounds.

[0592] The light-emitting layer includes luminescent dyes (i.e., dopants) that can emit different wavelengths of light, and may also include a host material. Depending on the technology, the light-emitting layer material can be different materials such as fluorescent electroluminescent materials, phosphorescent electroluminescent materials, and thermally activated delayed fluorescence materials. In a tandem OLED device, a single light-emitting technology can be used, or a combination of multiple different light-emitting technologies can be used. These different light-emitting materials, classified by technology, can emit light of the same color or different colors of light.

[0593] The OLED organic material layer also includes an electron transport region. The electron transport region can be a single-layer electron transport layer (ETL), i.e., a single-layer electron transport layer containing only one compound or a single-layer electron transport layer containing multiple compounds. Alternatively, the electron transport region can be a multilayer structure including at least one of an electron injection layer (EIL), an electron transport layer (ETL), and a hole blocking layer (HBL).

[0594] In the tandem OLED device described in this invention, each light-emitting unit consists of a hole transport region, a light-emitting layer, and an electron transport region. Multiple light-emitting units are connected in series by a connecting layer. The light-emitting unit can be a monochromatic light-emitting unit that emits a single color such as red, green, or blue, or a monochromatic light-emitting unit that emits different colors such as red, green, and blue, or a single-color light-emitting layer that can emit different colors such as red, green, and blue simultaneously.

[0595] The interconnect layer in the tandem OLED device described in this invention is as follows: Figure 1 As shown, the first light-emitting unit is fabricated on the anode of the device. A connection layer 1 is fabricated between the first and second light-emitting units. The connection layer structure is an n-type doped layer / n-type layer / p-type layer. Then, a connection layer 2 and a third light-emitting unit are fabricated on the second light-emitting unit. According to the device structure design requirements, N-1 connection layers can be fabricated accordingly until the Nth light-emitting unit is fabricated. Finally, the device cathode is fabricated.

[0596] The n-type doped layer primarily employs n-type dopant and the o-phenanthroline-type electron-injection material described in this invention. The n-type dopant mainly consists of alkali metals, alkaline earth metals, and some transition metals and their salts, including but not limited to lithium (Li), sodium (Na), potassium (K), rubidium (Rb), cesium (Cs), and magnesium.

[0597] A mixture of one or more of the following: Mg, Ca, Fe, Cr, Nb, Co, Mn, Ni, Cu, Zn, Ag, Pd, Rh, Ru, Ir, W, Re, Pt, Au, and Yb. The doping ratio of the metallic n-type dopant in the n-type doped layer is from 0.1 wt% to 50 wt%, corresponding to a doping ratio of 0.01 vol% to 5 vol%, preferably 0.05 wt% to 20 wt%. Its total thickness is from 0.1 nm to 20 nm, more preferably 1-10 nm.

[0598] The n-type layer includes, but is not limited to, HATCN, etc.

[0599] The p-type layer mainly uses organic materials with hole transport properties, including but not limited to NPB, TAPC, TCTA, spiro-TAD, mCP, TPTE, BFA-IT, TDAB, TDAPB, PTDATA, 2-TNATA, mCBP, etc.

[0600] The fabrication process of the tandem organic electroluminescent device in the embodiments of the present invention is as follows:

[0601] Specifically, the tandem OLED device used in this experiment is a dual-emitting-layer device with a connecting layer. The device fabrication process is as follows: a glass plate coated with an ITO transparent conductive layer is ultrasonically treated in a commercial cleaning agent, rinsed in deionized water, ultrasonically degreased in an acetone:ethanol mixed solvent, baked in a clean environment until all moisture is removed, cleaned with ultraviolet light and ozone, and bombarded with a low-energy cation beam;

[0602] The glass substrate with the anode was placed in a vacuum chamber and evacuated to a vacuum level of 1×10⁻⁶. -5 ~5×10 -4 Pa, HATCN is vacuum-deposited as a hole injection layer on the above-mentioned anodic layer film at a deposition rate of 0.05 nm / s and a film thickness of 5 to 10 nm.

[0603] NPB was vacuum-deposited on top of the hole injection layer as the hole transport layer of the device at a deposition rate of 0.1 nm / s and a total film thickness of 30 to 50 nm.

[0604] The light-emitting layer of the device is vacuum-deposited on top of the hole transport layer. The light-emitting layer of this invention includes a host material Be(bq)₂ and a phosphorescent dye Ir(mphmq)₂(tmd). Doping is performed using a multi-source co-evaporation method, with the rate and doping concentration controlled by high and low crystal oscillator probes. The evaporation rate of the host material is adjusted to 0.1 nm / s, and the evaporation rate of the dye in the light-emitting layer is adjusted to 1% to 5% of the host evaporation rate, thereby achieving a predetermined doping ratio. The total film thickness of the light-emitting layer is 20 to 50 nm.

[0605] DPPyA was vacuum-deposited on top of the light-emitting layer as an electron transport layer material at a deposition rate of 0.1 nm / s and a total film thickness of 20 to 60 nm.

[0606] A connection layer with a total thickness of 20 to 10 nm is vacuum-deposited on the electron transport layer (ETL). The n-type doped layer comprises metallic Ag and o-phenanthroline compounds of this specific structure, with in-situ doping achieved by adjusting their respective deposition rates. The deposition rate ratio of metallic Ag to organic material is 1%-10% (i.e., volume fraction between 0.1 vol% and 1 vol%), and the thickness is 10 nm. The n-type layer is HATCN, with a thickness of 10 nm, and the p-type layer is NPB, with a thickness of 75 nm.

[0607] A light-emitting layer with a total thickness of 20 to 50 nm and an electron transport layer of 20 to 60 nm are vacuum-deposited on the connecting layer. An electron injection layer is formed by simultaneously depositing metallic Ag and an o-phenanthroline compound of this specific structure as described in this invention on the electron transport layer (ETL). In-situ doping is achieved by adjusting the deposition rates of the respective materials, wherein the deposition rate ratio of metallic Ag to organic material is 1%-10% (i.e., volume fraction between 0.1 vol% and 1 vol%), while controlling the total thickness of the electron injection layer to 5 nm. Finally, 150 nm of Al is vacuum-deposited on the electron injection layer as the cathode of the device. A tandem OLED device with a dual light-emitting layer is then fabricated.

[0608] Table 2 below shows the organic compounds and their structural formulas used in the tandem OLED devices prepared according to the embodiments of the present invention.

[0609] Table 2:

[0610]

[0611]

[0612] Device Example 54

[0613] In this embodiment, a 10nm Ag:E-1 layer (with a deposition rate ratio of 3%) is used as the n-type doped layer in the bonding layer, and a 5nm Ag:E-1 layer (with a deposition rate ratio of 3%) is used as the electron injection layer. This results in the following structure:

[0614] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-1(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-1(3%,5nm) / / Al(150nm)

[0615] Device Example 55

[0616] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-6, and the Ag:E-6 evaporation rate ratio is 3%. The device structure is as follows:

[0617] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-6(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-6(3%,5nm) / Al(150nm)

[0618] Device Example 56

[0619] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-7, and the Ag:E-7 evaporation rate ratio is 3%. The device structure is as follows:

[0620] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-7(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Ag:E-7(3%, 5nm) / Al(150nm).

[0621] Device Example 57

[0622] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-8, and the Ag:E-8 evaporation rate ratio is 3%. The device structure is as follows:

[0623] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-8(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-8(3%,5nm) / Al(150nm)

[0624] Device Example 58

[0625] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-9, and the Ag:E-9 deposition rate ratio is 3%. The device structure is as follows:

[0626] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-9(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-9(3%,5nm) / Al(150nm)

[0627] Device Example 59

[0628] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-16, and the Ag:E-16 evaporation rate ratio is 3%. The device structure is as follows:

[0629] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-16(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-16(3%,5nm) / Al(150nm)

[0630] Device Example 60

[0631] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-17, and the Ag:E-17 evaporation rate ratio is 3%. The device structure is as follows:

[0632] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-17(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-17(3%,5nm) / Al(150nm)

[0633] Device Example 61

[0634] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-18, and the Ag:E-18 evaporation rate ratio is 3%. The device structure is as follows:

[0635] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-18(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-18(3%,5nm) / Al(150nm)

[0636] Device Example 62

[0637] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-19, and the Ag:E-19 deposition rate is 3%. The device structure is as follows:

[0638] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-19(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-19(3%,5nm) / Al(150nm)

[0639] Device Example 63

[0640] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-37, and the Ag:E-37 evaporation rate is 3%. The device structure is as follows:

[0641] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-37(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-37(3%,5nm) / Al(150nm)

[0642] Device Example 64

[0643] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-42 with an Ag:E-42 deposition rate ratio of 3%. The device structure is as follows:

[0644] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-42(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-42(3%,5nm) / Al(150nm)

[0645] Device Example 65

[0646] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-45, and the Ag:E-45 evaporation rate ratio is 3%. The device structure is as follows:

[0647] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-45(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-45(3%,5nm) / Al(150nm)

[0648] Device Example 66

[0649] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-55, and the Ag:E-6 evaporation rate ratio is 3%. The device structure is as follows:

[0650] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-55(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-55(3%,5nm) / Al(150nm)

[0651] Device Example 57

[0652] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-73, and the Ag:E-73 deposition rate is 3%. The device structure is as follows:

[0653] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-73(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-73(3%,5nm) / Al(150nm)

[0654] Device Example 68

[0655] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-91, and the Ag:E-91 deposition rate is 3%. The device structure is as follows:

[0656] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-91(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-91(3%,5nm) / Al(150nm)

[0657] Device Example 69

[0658] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-109, and the Ag:E-109 evaporation rate ratio is 3%. The device structure is as follows:

[0659] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-109(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-109(3%,5nm) / Al(150nm)

[0660] Device Example 70

[0661] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-115, and the Ag:E-115 deposition rate is 3%. The device structure is as follows:

[0662] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-115(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-115(3%,5nm) / Al(150nm)

[0663] Device Example 71

[0664] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-125, and the Ag:E-125 deposition rate is 3%. The device structure is as follows:

[0665] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-125(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-125(3%,5nm) / Al(150nm)

[0666] Device Example 72

[0667] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-142, and the Ag:E-142 deposition rate is 3%. The device structure is as follows:

[0668] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-142(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-142(3%,5nm) / Al(150nm)

[0669] Device Example 73

[0670] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-148, and the Ag:E-148 evaporation rate is 3%. The device structure is as follows:

[0671] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-148(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-148(3%,5nm) / Al(150nm)

[0672] Device Example 74

[0673] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-158, and the Ag:E-158 evaporation rate is 3%. The device structure is as follows:

[0674] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-158(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-158(3%,5nm) / Al(150nm)

[0675] Device Example 75

[0676] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-175, and the Ag:E-175 deposition rate is 3%. The device structure is as follows:

[0677] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-175(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-175(3%,5nm) / Al(150nm)

[0678] Device Example 76

[0679] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-192, and the Ag:E-192 deposition rate is 3%. The device structure is as follows:

[0680] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-192(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-192(3%,5nm) / Al(150nm)

[0681] Device Example 77

[0682] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-209, and the Ag:E-209 evaporation rate ratio is 3%. The device structure is as follows:

[0683] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-209(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-209(3%,5nm) / Al(150nm)

[0684] Device Example 78

[0685] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-279, and the Ag:E-279 evaporation rate is 3%. The device structure is as follows:

[0686] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-279(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-279(3%,5nm) / Al(150nm)

[0687] Device Example 79

[0688] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-349, and the Ag:E-349 evaporation rate is 3%. The device structure is as follows:

[0689] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-349(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-349(3%,5nm) / Al(150nm)

[0690] Device Example 80

[0691] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-357, and the Ag:E-357 evaporation rate is 3%. The device structure is as follows:

[0692] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-357(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-357(3%,5nm) / Al(150nm)

[0693] Device Example 81

[0694] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-421, and the Ag:E-421 evaporation rate is 3%. The device structure is as follows:

[0695] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-421(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-421(3%,5nm) / Al(150nm)

[0696] Device Example 82

[0697] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-427, and the Ag:E-427 evaporation rate is 3%. The device structure is as follows:

[0698] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-427(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-427(3%,5nm) / Al(150nm)

[0699] Device Example 83

[0700] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-626, and the Ag:E-626 evaporation rate is 3%. The device structure is as follows:

[0701] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-626(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-626(3%,5nm) / Al(150nm)

[0702] Device Example 84

[0703] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-631, and the Ag:E-631 deposition rate is 3%. The device structure is as follows:

[0704] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-631(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-631(3%,5nm) / Al(150nm)

[0705] Device Example 85

[0706] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-634, and the Ag:E-634 deposition rate is 3%. The device structure is as follows:

[0707] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-634(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-634(3%,5nm) / Al(150nm)

[0708] Device Example 86

[0709] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-644, and the Ag:E-644 evaporation rate is 3%. The device structure is as follows:

[0710] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-644(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-644(3%,5nm) / Al(150nm)

[0711] Device Example 87

[0712] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-652, and the Ag:E-652 deposition rate is 3%. The device structure is as follows:

[0713] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-652(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-652(3%,5nm) / Al(150nm)

[0714] Device Example 88

[0715] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-662, and the Ag:E-662 deposition rate is 3%. The device structure is as follows:

[0716] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-662(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-662(3%,5nm) / Al(150nm)

[0717] Device Example 89

[0718] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-667, and the Ag:E-667 evaporation rate is 3%. The device structure is as follows:

[0719] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-667(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-667(3%,5nm) / Al(150nm)

[0720] Device Example 90

[0721] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-670, and the Ag:E-670 deposition rate is 3%. The device structure is as follows:

[0722] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-670(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-670(3%,5nm) / Al(150nm)

[0723] Device Example 91

[0724] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-680, and the Ag:E-680 evaporation rate is 3%. The device structure is as follows:

[0725] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-680(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-680(3%,5nm) / Al(150nm)

[0726] Device Example 92

[0727] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-698 with an Ag:E-698 deposition rate ratio of 3%. The device structure is as follows:

[0728] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-698(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-698(3%,5nm) / Al(150nm)

[0729] Device Example 93

[0730] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-705, and the Ag:E-705 deposition rate is 3%. The device structure is as follows:

[0731] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-705(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-705(3%,5nm) / Al(150nm)

[0732] Device Example 94

[0733] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-715, and the Ag:E-715 deposition rate is 3%. The device structure is as follows:

[0734] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-715(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-715(3%,5nm) / Al(150nm)

[0735] Device Example 95

[0736] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-722, and the Ag:E-722 deposition rate is 3%. The device structure is as follows:

[0737] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-722(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-722(3%,5nm) / Al(150nm)

[0738] Device Example 96

[0739] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-732, and the Ag:E-732 deposition rate is 3%. The device structure is as follows:

[0740] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-732(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-732(3%,5nm) / Al(150nm)

[0741] Device Example 97

[0742] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-739, and the Ag:E-739 evaporation rate is 3%. The device structure is as follows:

[0743] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-739(3%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-739(3%,5nm) / Al(150nm)

[0744] Device Example 98

[0745] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Ag:E-749, and the Ag:E-749 deposition rate is 3%. The device structure is as follows:

[0746] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-749(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Ag:E-749(3%, 5nm) / Al(150nm).

[0747] Device Example 99

[0748] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Yb:E-1, and the Yb:E-1 deposition rate ratio is 3%. The device structure is as follows:

[0749] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Yb:E-1(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Yb:E-1(3%, 5nm) / Al(150nm).

[0750] Device Example 100

[0751] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Zn:E-1, and the Zn:E-1 deposition rate ratio is 3%. The device structure is as follows:

[0752] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Zn:E-1(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Zn:E-1(3%, 5nm) / Al(150nm).

[0753] Device Example 101

[0754] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Yb:E-9, and the Yb:E-9 evaporation rate ratio is 3%. The device structure is as follows:

[0755] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Yb:E-9(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Yb:E-9(3%, 5nm) / Al(150nm).

[0756] Device Example 102

[0757] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Zn:E-9, and the Zn:E-9 evaporation rate ratio is 3%. The device structure is as follows:

[0758] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Zn:E-9(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Zn:E-9(3%, 5nm) / Al(150nm).

[0759] Device Example 103

[0760] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Yb:E-626, and the Yb:E-626 evaporation rate ratio is 3%. The device structure is as follows:

[0761] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Yb:E-626(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Yb:E-626(3%, 5nm) / Al(150nm).

[0762] Device Example 104

[0763] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Zn:E-626, and the Zn:E-626 evaporation rate ratio is 3%. The device structure is as follows:

[0764] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Zn:E-626(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Zn:E-626(3%, 5nm) / Al(150nm).

[0765] Device Example 105

[0766] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Yb:E-634, and the Yb:E-634 deposition rate is 3%. The device structure is as follows:

[0767] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Yb:E-634(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Yb:E-634(3%, 5nm) / Al(150nm).

[0768] Device Example 106

[0769] The preparation method is the same as in Example 54, except that the n-type doped layer and electron injection layer materials are replaced with Zn:E-634, and the Zn:E-634 evaporation rate ratio is 3%. The device structure is as follows:

[0770] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Zn:E-634(3%,10nm) / HAT CN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%, 24nm) / DPPyA(40nm) / Zn:E-634(3%, 5nm) / Al(150nm).

[0771] Comparative Device Example 8

[0772] The preparation method is the same as in Example 46, except that the n-type dopant in the n-type doped layer and electron injection layer materials is replaced with Cs₂CO₃, wherein the evaporation rate ratio of Cs₂CO₃:E⁻¹ is 10%. The device structure is as follows:

[0773] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Cs2CO3:E-1(10%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Cs2CO3:E-1(10%,5nm) / Al(150nm)

[0774] Comparative Device Example 9

[0775] The preparation method is the same as in Example 46, except that the electron injection layer material is replaced with the existing compound LiF (1 nm). The device structure is as follows:

[0776] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-1(3%,10nm) / HATCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / LiF(1nm) / Al(150nm)

[0777] Comparative Device Example 10

[0778] The preparation method is the same as in Example 46, except that the electron injection layer material is replaced with the existing compound Liq (1 nm). The device structure is as follows:

[0779] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:E-1(3%,10nm) / HATCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Liq(1nm) / Al(150nm)

[0780] Comparative Device Example 11

[0781] The preparation method is the same as in Example 46, except that the n-type doped layer and electron injection layer materials are replaced with Ag:D-1, and the Ag:D-1 deposition rate ratio is 10%. The device structure is as follows:

[0782] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:D-1(10%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:D-1(10%,5nm) / Al(150nm)

[0783] Comparative Device Example 12

[0784] The preparation method is the same as in Example 46, except that the n-type doped layer and electron injection layer materials are replaced with Ag:D-2, and the Ag:D-2 deposition rate ratio is 10%. The device structure is as follows:

[0785] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:D-2(10%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Ag:D-2(10%,5nm) / Al(150nm)

[0786] Comparative Device Example 13

[0787] The preparation method is the same as in Example 46, except that the n-type doped layer and electron injection layer materials are replaced with Yb:D-2, and the Yb:D-2 deposition rate ratio is 10%. The device structure is as follows:

[0788] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Yb:D-2(10%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Yb:D-2(10%,5nm) / Al(150nm)

[0789] Comparative Device Example 14

[0790] The preparation method is the same as in Example 46, except that the n-type doped layer and electron injection layer materials are replaced with Zn:D-2, and the Zn:D-2 deposition rate ratio is 10%. The device structure is as follows:

[0791] ITO / HATCN(5nm) / NPB(35nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Zn:D-2(10%,10nm) / HA TCN(10nm) / NPB(75nm) / Be(bq)2:Ir(mphmq)2(tmd)(5%,24nm) / DPPyA(40nm) / Zn:D-2(10%,5nm) / Al(150nm)

[0792] The performance of the organic electroluminescent devices prepared by the above-mentioned device embodiments and comparative device embodiments is shown in Table 2 below.

[0793] Table 2:

[0794]

[0795]

[0796] A comparison of Comparative Examples 8 to 10 with Example 54 reveals that, with other materials remaining the same in the tandem organic light-emitting device structure, the OLED devices prepared with the compounds of the present invention exhibit lower voltage rise values ​​after 24 hours of operation compared to those prepared with the prior art compounds in Comparative Examples 8 to 10. Simultaneously, the stability of the devices is significantly improved, and the device lifetime is correspondingly increased. It is speculated that during the heating and evaporation process and during device operation, alkali metal ions generated in the alkali metal n-type dopant and cathode interface material may migrate or diffuse into the p-shaped layer or the light-emitting layer, leading to aging of the bonding layer and exciton quenching in the light-emitting layer, thereby reducing the device efficiency and lifetime.

[0797] The prior art compound D1 used in Comparative Example 11 is 4,7-diphenyl-o-phenanthroline (Bphen), a commonly used electron transport material. It possesses excellent coordination properties and, after Ag doping, can serve as an efficient electron injection layer and an n-type doped layer in existing technologies. However, this compound has a molecular weight of only 332.41, resulting in a glass transition temperature of only 62°C and poor film stability, thus leading to a relatively low lifetime in Comparative Example 9.

[0798] The prior art compound D2 used in Comparative Examples 12, 13, and 14 is a commonly used electron transport material. A comparison with Examples 54, 99, and 100 using Compound E-1 of this invention shows that E1, by replacing the benzene ring as the bridging group with a spirofluorene group that has stronger transport performance, is more conducive to electron transport. The electron generation, transport, and injection performance of the n-type doped layer and electron injection layer materials using Ag:E1, Yb:E1, and Zn:E1 as the connecting layer of the series device is significantly better than that of Ag:D2, Yb:D2, and Zn:D2. Compared to D2, the device using E1 as the organic ligand has a lower voltage rise after 24 hours of operation and a longer lifetime. Further comparison of Examples 54 and Examples 54 to 61 reveals that, with consistent backbone groups, the stronger the electron-donating performance of R1 and R2, the stronger the coordination performance of the corresponding phenanthroline ligand, resulting in a better performance of the electron injection layer, which significantly reduces the device's driving voltage and improves its efficiency and lifetime. This also reflects that the selection of R1 and R2 in the core structure of the compound of the present invention has an important influence on the performance of this type of phenanthroline material when paired with a transition metal as an electron injection layer.

[0799] In summary, the connection layer design strategy proposed in this invention for novel tandem OLED devices, namely n-type doped layer / n-type layer / p-type layer, helps to suppress the diffusion and migration of metal-based n-type dopants in tandem OLED devices, helps to improve the stability of the connection layer and reduce exciton quenching in the light-emitting layer, and can therefore be applied to tandem OLED devices, helping the devices achieve a longer lifetime and lower voltage rise during operation.

[0800] The above embodiments are merely illustrative examples and are not intended to limit the implementation. Guided by the inventive concept, those skilled in the art can make various modifications and improvements, and other variations or alterations can be made based on the above description. Any obvious variations or alterations derived therefrom are still within the protection scope of this invention.

Claims

1. An organic compound having the structure shown in formula (1): （1） In equation (1), n ​​is 2; When Q is selected from any of the following: ； Ring C represents a benzene ring that is absent or fused with rings A and B. When ring C is absent, rings A and B are connected by a single bond. When Q is selected from the following formula: ； Ring C represents non-existence; Ring A and Ring B are connected by a single bond. R1, R2, R3, R4, and R5 are each independently selected from one of the following: hydrogen, C1-C30 chain alkyl, C3-C20 cycloalkyl, C1-C30 alkoxy, C6-C60 aryl, and C3-C60 heteroaryl. "—*" represents the connection site of Q in equation (1), and "—" represents the way the loop structure is expressed, indicating that the connection site is at any position on the loop structure where bonding can occur.

2. The organic compound according to claim 1, characterized by When Q is selected from the following formula: , ring C represents nothing, ring A and ring B are connected by a single bond; When Q is selected from the following structure: , ring C represents a phenyl ring fused to ring A, ring B or both, and when ring C is absent, ring A and ring B are connected by a single bond; R1, R2, R3, R4, and R5 are each independently selected from one of the following: C1-C10 chain alkyl, C3-C10 cycloalkyl, C6-C30 arylamino, C6-C60 aryl, and C3-C60 heteroaryl.

3. The organic compound according to claim 1 or 2, characterized in that, R1, R2, R3, R4, and R5 are independently selected from methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, 2-methylbutyl, n-pentyl, sec-pentyl, cyclopentyl, neopentyl, n-hexyl, cyclohexyl, neohexyl, n-heptyl, cycloheptyl, n-octyl, cyclooctyl, tetrahydropyrrolyl, piperidinyl, methoxy, ethoxy, propoxy, butoxy, phenoxy, phenyl, naphthyl, anthracene, benzo[a]anthrayl, phenanthryl, benzo[a]phenanthryl, pyrene, pyryl, peryl, fluoranyl, tetraphenyl, pentaphenyl, benzo[a]pyrene, biphenyl, terphenyl, triphenyl, tetraphenyl, and tetraphenyl. , fluorenyl, spirodifluorenyl, dihydrophenanthrene, dihydropyrene, tetrahydropyrene, cis or trans indofluorenyl, furanyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, thiopheneyl, benzothiopheneyl, isobenzothiopheneyl, dibenzothiopheneyl, pyrroleyl, isoindolyl, carbazoleyl, tert-butylcarbazoleyl, indocarbazoleyl, tetrahydroacridyl, indazoleyl, oxazolyl, benzoxazolyl, naphthoxazolyl, anthrazoxazolyl, benzoxazolyl, naphthoxazolyl, anthrazoxazolyl, phenanthroxazolyl, 1,2-thiazolyl, 1,3-thiazolyl, benzothiazolyl, 1,5-diazaanthrayl, 2, One of 7-diazapyrene, 2,3-diazapyrene, 1,6-diazapyrene, 1,8-diazapyrene, 4,5-diazapyrene, 4,5,9,10-tetraazapyrene, pyrazinyl, phenazinyl, phenoxazinyl, phenthiazinyl, naphridinyl, azacarbazolyl, benzocarbazolyl, phenanthrolinel, purinel, pteridinyl, inazinyl, 1,5,7-triazabicyclo[4.4.0]dec-5-enyl, and 4-methoxyphenyl.

4. An organic compound selected from compounds with the following specific structures: 。 5. The use of the organic compound according to any one of claims 1-4 as a functional material in an organic electronic device, said organic electronic device being selected from organic electroluminescent devices, optical sensors, solar cells, or organic thin-film transistors.

6. The organic compound of any one of claims 1-4 is used as a dopant and / or electron injection material in an organic electroluminescent device.

7. The organic compound of any one of claims 1-4 is used as an electron injection material in a single-junction organic light-emitting device, or as an n-type doped layer material and an electron injection material in a tandem organic light-emitting device.

8. A single-junction organic light-emitting device, comprising a substrate and an anode layer, a light-emitting functional layer, and a cathode layer sequentially formed on the substrate, characterized in that, The light-emitting functional layer includes a light-emitting layer and an electron injection layer, and further includes one or more of a hole injection layer, a hole transport layer, and an electron transport layer. The hole injection layer is formed on the anode layer, the hole transport layer is formed on the hole injection layer, the light-emitting layer is formed on the hole transport layer, the electron transport layer is formed on the light-emitting layer, the electron injection layer is formed on the electron transport layer, and the cathode layer is formed on the electron injection layer. The electron injection layer includes at least one organic compound as described in claim 1, and further includes an n-type dopant selected from at least one of alkali metals, alkaline earth metals, transition metals, and their salts. The doping ratio of the n-type dopant in the electron injection layer to the organic compound of claim 1 is from 0.1 wt% to 50 wt%.

9. The single-junction organic electroluminescent device according to claim 8, characterized in that, The n-type dopant in the electron injection layer is selected from one or a mixture of several of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, iron, chromium, niobium, cobalt, manganese, nickel, copper, zinc, silver, palladium, rhodium, ruthenium, iridium, tungsten, rhenium, platinum, gold, and ytterbium; The doping ratio of the n-type dopant in the electron-injected layer to the organic compound of claim 1 is from 0.05 wt% to 20 wt%.

10. The single-junction organic electroluminescent device according to claim 8, characterized in that, The thickness of the electron injection layer is 0.1 nm to 20 nm.

11. The single-junction organic electroluminescent device according to claim 8, characterized in that, The thickness of the electron injection layer is 3-5 nm.

12. A series organic electroluminescent device, comprising the following structure: an anode, a cathode, two electroluminescent units disposed between the anode and the cathode, a connecting layer disposed between two adjacent electroluminescent units, an electron injection layer disposed between the light-emitting unit closer to the cathode and the cathode, and each electroluminescent unit comprising an electron transport layer and an organic light-emitting layer; Its features are: The connecting layer has a multi-layer structure, including an n-type doped layer, an n-type layer, and a p-type layer; At least one of the n-type doped layer and the electron injection layer comprises at least one organic compound of claim 1.

13. The tandem organic electroluminescent device according to claim 12, characterized in that, Both the n-type doped layer and the electron injection layer contain at least one organic compound as described in claim 1.

14. The tandem organic electroluminescent device according to claim 12, characterized in that, The n-type doped layer in the electron injection layer and the connecting layer further includes an n-type dopant, which is selected from at least one of alkali metals, alkaline earth metals, transition metals and their salts. The doping ratio of the n-type dopant in the n-type doped layer of the electron injection layer and the linking layer to the organic compound of claim 1 is from 0.1 wt% to 50 wt%.

15. The tandem organic electroluminescent device according to claim 14, characterized in that, The n-type dopant is selected from one or a mixture of several of lithium, sodium, potassium, rubidium, cesium, magnesium, calcium, iron, chromium, niobium, cobalt, manganese, nickel, copper, zinc, silver, palladium, rhodium, ruthenium, iridium, tungsten, rhenium, platinum, gold, and ytterbium; The doping ratio of the n-type dopant to the organic compound of claim 1 is from 0.05 wt% to 20 wt%.

16. The tandem organic electroluminescent device according to claim 12, characterized in that, The thickness of the electron injection layer is 0.1 nm-20 nm, and the thickness of the n-type doped layer in the connecting layer is 0.1 nm-20 nm.

17. The tandem organic electroluminescent device according to claim 12, characterized in that, The thickness of the electron injection layer is 3-5 nm, and the thickness of the n-type doped layer in the connecting layer is 1-10 nm.

Images